CN115291450A - Method for printing electrolyte layer, electrochromic device and preparation method thereof - Google Patents
Method for printing electrolyte layer, electrochromic device and preparation method thereof Download PDFInfo
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- CN115291450A CN115291450A CN202210999274.0A CN202210999274A CN115291450A CN 115291450 A CN115291450 A CN 115291450A CN 202210999274 A CN202210999274 A CN 202210999274A CN 115291450 A CN115291450 A CN 115291450A
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- electrochromic device
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 131
- 238000007639 printing Methods 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000003085 diluting agent Substances 0.000 claims abstract description 70
- 239000002002 slurry Substances 0.000 claims abstract description 46
- 238000007650 screen-printing Methods 0.000 claims abstract description 33
- 230000008569 process Effects 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 238000001723 curing Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000004014 plasticizer Substances 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims description 8
- 159000000002 lithium salts Chemical class 0.000 claims description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 8
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 239000004417 polycarbonate Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 125000004386 diacrylate group Chemical group 0.000 claims description 5
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 5
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 5
- 229920000515 polycarbonate Polymers 0.000 claims description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- 238000000016 photochemical curing Methods 0.000 claims description 4
- 229920002620 polyvinyl fluoride Polymers 0.000 claims description 4
- 238000001029 thermal curing Methods 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 3
- 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 3
- SYENVBKSVVOOPS-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl prop-2-enoate Chemical compound CCC(CO)(CO)COC(=O)C=C SYENVBKSVVOOPS-UHFFFAOYSA-N 0.000 claims description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 239000004971 Cross linker Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 description 107
- 238000004519 manufacturing process Methods 0.000 description 6
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical group C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 5
- 229920000671 polyethylene glycol diacrylate Polymers 0.000 description 5
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000005562 fading Methods 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002346 layers by function Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- G02F2001/164—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 the electrolyte is made of polymers
-
- 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
Abstract
The invention discloses a method for printing an electrolyte layer, an electrochromic device and a preparation method thereof, wherein the method for printing the electrolyte layer comprises the following steps: obtaining electrolyte slurry, and mixing the electrolyte slurry with a diluent to obtain an electrolyte diluent with the viscosity of 4000-40000mPa & s; printing the electrolyte diluent on the base material by adopting a screen printing mode to form a printing layer on the base material; removing the diluent in the printing layer to obtain a prefabricated layer; and curing the prefabricated layer to obtain the electrolyte layer. The method for printing the electrolyte layer can ensure that the viscosity of the electrolyte slurry meets the requirement of screen printing and can also keep the shape of the uncured electrolyte layer in the assembling process of the electrochromic device.
Description
Technical Field
The invention relates to the technical field of printed electronics, in particular to a method for printing an electrolyte layer, an electrochromic device and a preparation method thereof.
Background
One challenge for the industrial application of electrochromic devices is the large area green process fabrication, one of the major problems in this regard is the printing fabrication of large area electrolytes. The traditional grouting and blade coating method cannot achieve very accurate electrolyte layer preparation, and the flatness and uniformity of the electrolyte film layer cannot be reliably guaranteed. The problem can be solved by adopting a screen printing method to prepare the electrolyte layer, but in the assembling process of the electrochromic device, when the viscosity of the electrolyte slurry formula is too small, the shape retentivity of the electrochromic device in the assembling process is poor; when the viscosity of the electrolyte slurry formula is too high, the slurry screen plate has poor penetrability, and a corresponding pattern cannot be printed.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
An object of the present invention is to provide a method of printing an electrolyte layer, which can maintain the shape of an uncured electrolyte layer during the assembly of an electrochromic device while the viscosity of an electrolyte paste satisfies the requirements of screen printing.
Another object of the present invention is to provide an electrochromic device and a method for manufacturing the same.
To achieve the above object, an embodiment of the present invention provides a method of printing an electrolyte layer, including the steps of:
obtaining electrolyte slurry, and mixing the electrolyte slurry with a diluent to obtain an electrolyte diluent with the viscosity of 4000-40000mPa & s;
printing the electrolyte diluent on the base material by adopting a screen printing mode to form a printing layer on the base material;
removing the diluent in the printing layer to obtain a prefabricated layer; and
and curing the prefabricated layer to obtain the electrolyte layer.
In one or more embodiments of the invention, the viscosity of the pre-layer is greater than or equal to 80000mPa · s.
In one or more embodiments of the present invention, the step of removing the diluent in the printing layer includes:
and heating the printing layer to remove the diluent in the printing layer.
In one or more embodiments of the present invention, the curing process is a photo-curing process or a thermal curing process.
In one or more embodiments of the present invention, the diluent includes at least one of ethyl acetate, ethanol, and water.
In one or more embodiments of the present invention, the electrolyte slurry includes a polymer host, a plasticizer, a lithium salt, a photoinitiator, and a crosslinking agent.
In one or more embodiments of the present invention, the crosslinking agent is one of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, trimethylolpropane acrylate; and/or the presence of a gas in the gas,
the polymer body includes at least one of polymethyl methacrylate, polyvinyl fluoride, and polyurethane.
In one or more embodiments of the present invention, the lithium salt is at least one of lithium perchlorate and lithium bistrifluoromethanesulfonylimide; and/or the presence of a gas in the atmosphere,
the plasticizer includes at least one of polycarbonate, dimethyl carbonate, ethylene carbonate, and water.
The embodiment of the invention also provides a preparation method of the electrochromic device, which comprises the following steps:
obtaining electrolyte slurry, and mixing the electrolyte slurry with a diluent to obtain an electrolyte diluent with the viscosity of 4000-40000mPa & s;
printing the electrolyte diluent on the first electrode by adopting a screen printing mode to form a printing layer on the first electrode;
removing the diluent in the printing layer to obtain a prefabricated layer;
attaching the prefabricated layer on the first electrode to the second electrode; and
and curing the prefabricated layer to obtain the electrochromic device.
The embodiment of the invention provides an electrochromic device, which is prepared by adopting the preparation method of the electrochromic device.
Compared with the prior art, according to the method for printing the electrolyte layer, disclosed by the embodiment of the invention, the electrolyte slurry is mixed with the diluent, so that the viscosity of the electrolyte diluent meets the requirements of screen printing, after the screen printing, the diluent in the printing layer is removed, the viscosity of the printing layer is improved, the printing layer is in an incompletely cured state, the printing layer has certain rigidity and certain wettability, the shape of the printing layer can be maintained to inhibit the extension phenomenon in the attaching process, and the uncured electrolyte layer can be ensured to be in close contact with other functional layers.
Drawings
Fig. 1 is a flow chart of a method of printing an electrolyte layer according to an embodiment of the invention;
FIG. 2 is a schematic diagram of an electrochromic device according to an embodiment of the invention;
FIG. 3 is a schematic representation of the electrochromic device of example 1 in a faded, transparent state;
FIG. 4 is a schematic representation of the electrochromic device in example 1 in the colored state;
fig. 5 is a diagram showing a state where an electrolyte paste in an electrolyte layer is printed on a base material by a conventional screen printing method.
Detailed Description
The following detailed description of the present invention is provided in conjunction with the accompanying drawings, but it should be understood that the scope of the present invention is not limited to the specific embodiments.
As shown in fig. 1, the method of printing an electrolyte layer according to a preferred embodiment of the present invention includes the steps of:
and S11, obtaining electrolyte slurry, and mixing the electrolyte slurry with the diluent to obtain the electrolyte diluent with the viscosity of 4000-40000mPa & S.
The electrolyte paste may include a polymer host, a plasticizer, a lithium salt, a photoinitiator, and a crosslinking agent, among others. Specifically, the crosslinking agent is polyethylene glycol diacrylate. The polymer body may include at least one of polymethyl methacrylate and polyvinyl fluoride. The lithium salt is at least one of lithium perchlorate and lithium bis (trifluoromethanesulfonyl) imide. The plasticizer comprises at least one of polycarbonate, dimethyl carbonate, ethylene carbonate and water. The viscosity of the electrolyte slurry may be greater than or equal to 80000mPa · s.
Specifically, the diluent comprises at least one of ethyl acetate, ethanol and water. The diluent serves to dilute the electrolyte slurry so that the viscosity of the mixed electrolyte diluent is 4000 to 40000 mPas. To meet the requirements of screen printing. Wherein the boiling point of the diluent is lower than the boiling point of the plasticizer, and later removal of the diluent, e.g., by heating, ensures removal of the diluent as much as possible while preventing or avoiding as much as possible a decrease in the amount of plasticizer in the electrolyte slurry.
The diluent is selected so as to satisfy the following conditions:
first, after the diluent is removed at a later stage, the components in the preformed layer are made substantially the same as the components in the electrolyte slurry, with substantially the same being understood to mean that the components and corresponding amounts are substantially the same.
Secondly, the diluent itself does not affect the working properties of the electrolyte slurry or the finally formed electrolyte layer to some extent.
And S12, printing the electrolyte diluent on the base material by adopting a screen printing mode to form a printing layer on the base material.
And S13, removing the diluent in the printing layer to obtain the prefabricated layer.
Specifically, the step of removing the diluent in the printed layer may include:
and heating the printing layer to remove the diluent in the printing layer. Wherein, the heating temperature can be adjusted according to the selection of the diluent and the selection of each component in the electrolyte slurry. The temperature of heating may be at or about the boiling temperature of the diluent. In addition, the heating temperature is preferably set to avoid volatilization of other substances in the electrolyte slurry.
Wherein the viscosity of the preformed layer is greater than or equal to 80000 mPas. The prefabricated layer has certain rigidity, and the shape of the prefabricated layer can be kept to inhibit the extension phenomenon in the attaching process.
Here, the composition of the preliminary layer and the composition of the electrolyte slurry may be considered to be substantially the same or substantially the same.
And S14, solidifying the prefabricated layer to obtain an electrolyte layer.
Specifically, the curing treatment is a photo-curing treatment or a thermal curing treatment. For example, when the electrolyte slurry contains a photoinitiator and a polymer such as PEG-DA, the preformed layer may be cured by uv curing. When other components such as maleimide are contained in the electrolyte slurry, the prefabricated layer may be subjected to a curing process by means of a heat curing process.
Note that the electrolyte layer exists in three states, that is, a low viscous state, a high viscous state, and a solid state during the production process. Wherein, the low viscosity state corresponds to the state of electrolyte diluent, and mainly meets the viscosity requirement of screen printing. The high viscosity state corresponds to the state of the prefabricated layer, plays a role in inhibiting the extension phenomenon in the attaching process and provides certain rigidity for the prefabricated layer. The highly viscous state can be understood as a state of incomplete curing, which has a certain wettability to ensure that the prefabricated layer can be in close contact with other functional layers. The solid state is the state of the final electrolyte layer, and serves to connect different substrates (or laminates).
Embodiments of the present invention provide an electrochromic device, and in a specific embodiment, the electrochromic device may include a first transparent electrode, a first electrode, an electrolyte layer, a second electrode, and a second transparent electrode, which are sequentially stacked.
The first electrode may be considered as a counter electrode or an ion storage layer. The second electrode may be considered to be the working electrode. The material of the first transparent electrode and the second transparent electrode can be selected from ITO, IZO or Ag grids and the like. The material of the first electrode may be a functional material in which an electrochromic reaction may occur, such as thiophene and its variants. The material of the second electrode can be thiophene and its derivatives, tiO 2 MCCP, and the like.
In a specific embodiment, the present invention further provides a method for preparing the electrochromic device, including the following steps:
and S21, obtaining electrolyte slurry, and mixing the electrolyte slurry with the diluent to obtain the electrolyte diluent with the viscosity of 4000-40000mPa & S.
The electrolyte paste may include a polymer host, a plasticizer, a lithium salt, a photoinitiator, and a crosslinking agent, among others. Specifically, the crosslinking agent is polyethylene glycol diacrylate. The polymer body may include at least one of polymethyl methacrylate and polyvinyl fluoride. The lithium salt is at least one of lithium perchlorate and lithium bis (trifluoromethanesulfonyl) imide. The plasticizer includes at least one of polycarbonate, dimethyl carbonate, ethylene carbonate and water. The viscosity of the electrolyte slurry may be greater than or equal to 80000mPa · s. The photoinitiator can be 2,2-dimethoxy-2-phenylacetophenone.
Specifically, the diluent comprises at least one of ethyl acetate, ethanol and water. The diluent serves to dilute the electrolyte slurry so that the viscosity of the mixed electrolyte diluent is 4000 to 40000 mPas. To meet the requirements of screen printing.
The diluent is selected so as to satisfy the following conditions:
first, after the diluent is removed at a later stage, the components in the preformed layer are made substantially the same as the components in the electrolyte slurry as far as possible, and substantially the same is understood to mean that the components and the corresponding contents are substantially the same.
Secondly, the diluent itself does not affect the working properties of the electrolyte slurry or the finally formed electrolyte layer to some extent.
And S22, printing the electrolyte diluent on the first electrode by adopting a screen printing mode to form a printing layer on the first electrode.
And S23, removing the diluent in the printing layer to obtain the prefabricated layer.
Specifically, the step of removing the diluent in the printed layer may include:
and heating the printing layer to remove the diluent in the printing layer. Wherein, the heating temperature can be adjusted according to the selection of the diluent and the selection of each component in the electrolyte slurry.
Wherein the viscosity of the preformed layer is greater than or equal to 80000 mPas. The prefabricated layer has certain rigidity, and the shape of the prefabricated layer can be kept to inhibit the extension phenomenon in the attaching process.
Here, the composition of the preliminary layer and the composition of the electrolyte slurry may be considered to be substantially the same or substantially the same.
And S24, attaching the prefabricated layer on the first electrode to the second electrode.
In step S24, the preformed layer on the first electrode is bonded to the second electrode to form a semi-finished product, and in the bonding process, because the preformed layer has a high viscosity, i.e., greater than or equal to 80000mPa · S, the preformed layer has a certain rigidity, and can maintain its shape to suppress the pressing force generated by the first electrode and the second electrode in the bonding process, thereby preventing the preformed layer from extending.
The first electrode may be considered as a counter electrode or an ion storage layer in the electrochromic device, and the formation method may be a printing method. The second electrode may be considered as a working electrode and may be formed by inkjet printing/spin coating/screen printing, etc.
And S25, curing the prefabricated layer to obtain the electrochromic device.
Specifically, the curing treatment is a photo-curing treatment or a thermal curing treatment. For example, when the electrolyte slurry contains a photoinitiator and a polymer such as PEG-DA, the preformed layer may be cured by uv curing. When other components such as maleimide are contained in the electrolyte slurry, the prefabricated layer may be subjected to a curing process by means of a heat curing process.
The main electrochromic area of the electrochromic device prepared by the invention can be more than or equal to 10cm and 10cm. The size of the pixel point of the electrochromic device prepared based on the design method can reach 0.5mm by 0.5mm, and the electrochromic device based on the process can be printed with a large-area device of 10cm by 10cm (electrochromic area). Maximum wavelength transmittance difference: 30 to 40 percent; response transmittance of fading and coloring (change to 90% of maximum transmittance difference) response time of fading and coloring at-0.6v, 0.8v drive voltage: all for-0.5 s; the tinting and faded state hold times are >5h.
As shown in fig. 2, in a specific embodiment, the area size of the ITO/PEDOT/electrolyte/PProDOT/ITO electrochromic device (i.e., the darker portion in fig. 2) obtained by the preparation method of the present invention may be from 1.5mm × 1.5mm to 10cm × 10cm.550nm is the maximum light modulation wavelength, and the maximum wavelength transmittance difference: 30 to 40 percent; response time of discoloration and coloring at-0.6V, 0.8V drive voltage: -0.5 s; the tinting and fading state holding times are >5h. Wherein the thickness of the electrolyte layer is 50 μm, and the electrolyte formula is PMMA/PC/PEGDA/water/LiTFSi/2,2-dimethoxy-2-phenyl acetophenone.
In another specific embodiment, only a partial area of the electrochromic device manufactured by the manufacturing method of the present invention may be an electrochromic area, and at this time, the electrochromic area may be in a pattern shape (such as an animal shape, a smiling face, a figure (a triangle, a square, etc.), or other figures), and the pattern is formed by printing the electrolyte layer only at the position where color change is required by screen printing.
In other embodiments, the patterned electrochromic region may also be a layer of electrolyte (non-dot) formed after the electrolyte paste is cured. And the electrolyte layer is a smooth film which can be observed by naked eyes, and has no problems of obvious net mark residue and the like.
As shown in fig. 5, fig. 5 is a picture of an electrolyte layer printed by a conventional screen printing method. Because no diluent is added between the printed electrolyte layers, the viscosity of the electrolyte slurry is low, and the problems of net marks and wire drawing during printing on a substrate are reduced.
In addition, when the electrolyte layer is printed by the conventional screen printing method, the viscosity of the electrolyte layer before curing is not adjusted after printing, so that the uncured electrolyte layer is not rigid enough to be attached to other devices, and a desired pattern may not be maintained, thereby causing a pattern formed in an electrochromic region of an electrochromic device to be finally manufactured to be deformed, which may result in a defective product.
The method for printing the electrolyte layer, the electrochromic device and the method for manufacturing the same according to the present invention will be described in detail with reference to specific examples.
Example 1
And forming a first transparent electrode on the ITO material in a screen printing mode, and forming the first electrode on the first transparent electrode by using PEDOT in the screen printing mode. And selecting an ITO material to form a second transparent electrode in a screen printing mode, and forming the second electrode on the second transparent electrode by using a PPRODOT spin coating mode.
3g of PMMA (polymethyl methacrylate), 5g of PC (polycarbonate), 5g of PEG-DA (polyethylene glycol diacrylate), 2.8g of LiTFSi and 15mg of 2,2-dimethoxy-2-phenylacetophenone are weighed and uniformly stirred to obtain electrolyte slurry with the viscosity of 88000mPa & s. Then 0.8g of water and 3g of ethyl acetate were weighed and mixed with the electrolyte slurry to obtain an electrolyte diluent having a viscosity of 4000mPa · s.
And printing the electrolyte diluent on the first electrode by adopting a screen printing mode to obtain a printing layer. And heating the printing layer at 60 ℃ for 5min. And obtaining the prefabricated layer.
The second electrode was attached to the pre-fabricated layer and cured under UV conditions to obtain an electrochromic device as shown in fig. 3 and 4, in which the electrolyte layer had a thickness of 50 μm.
Wherein, fig. 3 is a schematic diagram of the electrochromic device in the fading transparent state of the electrochromic device in the embodiment 1, and fig. 4 is a schematic diagram of the electrochromic device in the coloring state of the electrochromic device in the embodiment 1. As can be seen from fig. 3 and 4, the color-changing pattern in the electrochromic device in example 1 is in the shape of a smile face, and the shape of the dielectric layer in the electrochromic device is in the shape of a smile face formed by dots, so that the color-changing pattern in the electrochromic device is in the shape of a smile face.
Example 2
And forming a first transparent electrode on the ITO material in a screen printing mode, and forming a first electrode on the first transparent electrode by using PEDOT in the screen printing mode. And (3) alternatively, a second transparent electrode is formed by taking a silver paste material in a screen printing mode, and the second electrode is formed on the second transparent electrode by using the PPRODOT in a spin coating mode.
4g of PMMA, 3g of EC (ethylene carbonate), 5g of PEG-DA, 2.8g of LiTFSi and 15mg of 2,2-dimethoxy-2-phenylacetophenone are weighed respectively and uniformly stirred to obtain electrolyte slurry with the viscosity of 90000 mPas. 0.8g of water and 4.5g of ethyl acetate were weighed out and mixed with the electrolyte slurry to obtain an electrolyte diluent having a viscosity of 4000 mPas.
And printing the electrolyte diluent on the first electrode by adopting a screen printing mode to obtain a printing layer. And heating the printing layer at 60 ℃ for 5min. And obtaining a prefabricated layer.
And attaching the second electrode to the prefabricated layer, and curing under the UV condition to obtain the electrochromic device, wherein the thickness of the electrolyte layer is 45 microns. The electrochromic device obtained in this example had substantially the same performance as the electrochromic device obtained in example 1.
Example 3
And forming a first transparent electrode on the ITO material in a screen printing mode, and forming the first electrode on the first transparent electrode by using PEDOT in the screen printing mode. And selecting an ITO material to form a second transparent electrode in a screen printing mode, and forming the second electrode on the second transparent electrode by using a PPRODOT spin coating mode.
3g of PVDF (polyvinylidene fluoride), 5g of DEC (diethyl carbonate), 5g of PEG-DA, 2.8g of lithium perchlorate and 15mg of 2,2-dimethoxy-2-phenylacetophenone were weighed out and stirred uniformly to obtain an electrolyte slurry having a viscosity of 70000 mPas. Then 0.8g of water and 3g of ethyl acetate were weighed and mixed with the electrolyte slurry to obtain an electrolyte diluent having a viscosity of 4000mPa · s.
And printing the electrolyte diluent on the first electrode by adopting a screen printing mode to obtain a printing layer. And heating the printing layer at 60 ℃ for 5min. And obtaining a prefabricated layer.
And (3) attaching the second electrode to the prefabricated layer, and curing under the UV condition to obtain the electrochromic device, wherein the thickness of the electrolyte layer is 40 micrometers.
The electrochromic device obtained in this example had substantially the same performance as the electrochromic device obtained in example 1.
In summary, the preparation method of the electrochromic device of the invention has the following beneficial effects:
(1) The viscosity requirement of screen printing can be met by the electrolyte slurry through the diluent, the diluent is removed through subsequent steps, the viscosity of the system of the electrolyte layer before solidification is increased, the electrolyte layer has certain rigidity before solidification, and the shape of the electrolyte layer can be kept to inhibit the extension phenomenon in the laminating process.
(2) The effect of stably and efficiently printing the electrolyte layer in a large area is realized, the film thickness is uniform, the repeatability is good, the film thickness is very thin, and the performance of the electrochromic device can be further improved.
(3) By adding the thinner, the thickness of the printed electrolyte layer film can be effectively adjusted.
(4) The electrochromic device structure has the advantages of quick response and stable cycle.
The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (10)
1. A method of printing an electrolyte layer comprising the steps of:
obtaining electrolyte slurry, and mixing the electrolyte slurry with the diluent to obtain an electrolyte diluent with the viscosity of 4000-40000mPa & s;
printing the electrolyte diluent on the base material by adopting a screen printing mode to form a printing layer on the base material;
removing the diluent in the printing layer to obtain a prefabricated layer; and
and curing the prefabricated layer to obtain the electrolyte layer.
2. The method of printing an electrolyte layer of claim 1 wherein the viscosity of the pre-layer is greater than or equal to 80000 mPa-s.
3. The method of printing an electrolyte layer according to claim 1 wherein the step of removing the diluent in the printed layer comprises:
and heating the printing layer to remove the diluent in the printing layer.
4. The method of printing an electrolyte layer according to claim 1 wherein the curing process is a photo-curing process or a thermal curing process.
5. The method of printing an electrolyte layer of claim 1 wherein the diluent comprises at least one of ethyl acetate, ethanol, water.
6. The method of printing an electrolyte layer of claim 5 wherein the electrolyte paste comprises a polymer host, a plasticizer, a lithium salt, a photoinitiator, and a crosslinker, wherein the diluent has a boiling point lower than the boiling point of the plasticizer.
7. The method of printing an electrolyte layer of claim 6 wherein the cross-linking agent is one of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, trimethylolpropane acrylate; and/or the presence of a gas in the atmosphere,
the polymer body includes at least one of polymethyl methacrylate, polyvinyl fluoride, and polyurethane.
8. The method of printing an electrolyte layer of claim 6 wherein the lithium salt is at least one of lithium perchlorate and lithium bis (trifluoromethanesulfonyl) imide; and/or the presence of a gas in the atmosphere,
the plasticizer includes at least one of polycarbonate, dimethyl carbonate, diethyl carbonate, ethylene carbonate, and water.
9. The preparation method of the electrochromic device is characterized by comprising the following steps of:
obtaining electrolyte slurry, and mixing the electrolyte slurry with a diluent to obtain an electrolyte diluent with the viscosity of 4000-40000mPa & s;
printing the electrolyte diluent on the first electrode by adopting a screen printing mode to form a printing layer on the first electrode;
removing the diluent in the printing layer to obtain a prefabricated layer;
attaching the prefabricated layer on the first electrode to the second electrode; and
and curing the prefabricated layer to obtain the electrochromic device.
10. An electrochromic device, characterized in that it is produced by a method of producing an electrochromic device according to claim 9.
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