Disclosure of Invention
Aiming at least part of defects and shortcomings in the prior art, the embodiment of the invention provides a preparation method of laminated color-changing glass, which is used for solving the problem that lithium ions can be injected into and extracted from a color-changing layer periodically, ensuring high ion mobility and prolonging the service life and stability of the color-changing laminated glass.
In one aspect, an embodiment of the present invention provides a method for preparing a laminated color-changing glass, including:
providing a first glass substrate, a second glass substrate and a liquid electrolyte respectively;
Applying a first conductive layer to the first glass substrate by using one or a combination of at least two of a semiconductor oxide material, a metal material or an organic conductive material as a raw material, and
Using one or at least two oxides in W, mo, nb, ti, ta as raw materials, and laying the main color-changing layer on the first conductive layer to obtain first coated glass;
applying a second conductive layer to the second glass substrate by using one or a combination of at least two of a semiconductor oxide material, a metal material or an organic conductive material as a raw material, and
Using one or at least two oxides in Ni, V, co, ir, fe, mn as raw materials, and laying the auxiliary color-changing layer on the second conductive layer to obtain second coated glass;
Laminating the first coated glass and the second coated glass to form a glass interlayer;
injecting the liquid electrolyte between the main color-changing layer and the auxiliary color-changing layer in the glass interlayer to serve as an ion conductor layer;
forming the glass interlayer containing the ion conductor layer to obtain the interlayer color-changing glass;
Wherein the liquid electrolyte comprises a lithium-containing compound, an organic solvent and a high molecular polymer, the organic solvent being used for dissolving the high molecular polymer;
The lithium-containing compound is one or a combination of at least two of LiAsF6、LiPF6、LiBF4、CF3LiO3 S and LiClO4;
the high molecular polymer is one or a combination of at least two of polypropylene carbonate, polyaniline, polyethylene oxide, polyacrylonitrile, polyphenyl ether, polyvinylidene fluoride-hexafluoropropylene, polymethyl methacrylate, polyvinyl chloride and polyacrylonitrile-methyl acrylate copolymer;
the organic solvent is one or a combination of at least two of propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, methyl formate, methyl acrylate, methyl butyrate and ethyl acetate.
In another aspect, an embodiment of the present invention provides another method for preparing a laminated color-changing glass, including:
Preparing a first coated glass, a second coated glass and a liquid electrolyte respectively;
Laminating the first coated glass and the second coated glass to form a glass interlayer;
Injecting the liquid electrolyte into the glass interlayer to serve as an ion conductor layer;
forming the glass interlayer containing the ion conductor layer to obtain the interlayer color-changing glass;
Wherein the liquid electrolyte comprises a lithium-containing compound, an organic solvent and a high molecular polymer, and the organic solvent is used for dissolving the high molecular polymer.
In one embodiment, the preparing the first coated glass and the second coated glass separately includes:
providing a first glass substrate and a second glass substrate;
applying a first conductive layer on the first glass substrate, and applying a main color-changing layer on the first conductive layer to obtain the first coated glass, and
Laying a second conductive layer on the second glass substrate, and laying an auxiliary color-changing layer on the second conductive layer to obtain the second coated glass;
The injecting the liquid electrolyte into the glass interlayer as an ion conductor layer includes:
And injecting the liquid electrolyte between the main color-changing layer and the auxiliary color-changing layer to serve as the ion conductor layer.
In one embodiment, the applying the first conductive layer on the first glass substrate includes:
Using one or a combination of at least two of a semiconductor oxide material, a metal material or an organic conductive material as a raw material, and laying the first conductive layer on the first glass substrate;
the laying of the second conductive layer on the second glass substrate comprises:
and taking one or a combination of at least two of a semiconductor oxide material, a metal material or an organic conductive material as a raw material, and laying the second conductive layer on the second glass substrate.
In one embodiment, the applying a main color-changing layer on the first conductive layer includes:
and using one or at least two oxides in W, mo, nb, ti, ta as raw materials, and laying the main color-changing layer on the first conductive layer.
In one embodiment, the applying an auxiliary color-changing layer on the second conductive layer includes:
and using one or more oxides of Ni, V, co, ir, fe, mn as raw materials, and laying the auxiliary color-changing layer onto the second conductive layer.
In one embodiment, the lithium-containing compound is one or a combination of at least two of LiAsF6、LiPF6、LiBF4、CF3LiO3 S and LiClO4.
In one embodiment, the high molecular polymer is one or a combination of at least two of polypropylene carbonate, polyaniline, polyethylene oxide, polyacrylonitrile, polyphenylene ether, polyvinylidene fluoride-hexafluoropropylene, polymethyl methacrylate, polyvinyl chloride, and polyacrylonitrile-methyl acrylate copolymer.
In one embodiment, the organic solvent is one or a combination of at least two of propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, methyl formate, methyl acrylate, methyl butyrate, and ethyl acetate.
In one embodiment, the shaping process includes heating the glass interlayer containing the ion conductor layer to form a first transition layer between the primary color-changing layer and the ion conductor layer and a second transition layer between the secondary color-changing layer and the ion conductor layer.
The preparation method of the laminated glass disclosed by the embodiment of the invention has the beneficial effects that the possible problems of lithium ions in periodically injecting and extracting the color-changing layer can be solved, so that the laminated color-changing glass has the advantages of good color-changing effect, long service life, good stability and the like.
Detailed Description
The following description of the embodiments of the present invention will be made more fully hereinafter with reference to the accompanying drawings and detailed description, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that all directional indicators (such as up, down, left, right, front, and rear are used in the embodiments of the present invention) are merely for explaining the relative positional relationship, movement conditions, and the like between the components in a certain specific posture (as shown in the drawings), and if the specific posture is changed, the directional indicators are changed accordingly.
In the description of the present invention, it should also be noted that, unless explicitly specified and limited otherwise, the terms "disposed," "mounted," "connected," and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, integrally connected, mechanically connected, electrically connected, directly connected, indirectly connected through an intermediary, or in communication between two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
Some embodiments of the present invention are described in detail below with reference to the accompanying drawings. The embodiments described below and features of the embodiments may be combined with each other without conflict.
As shown in fig. 1, one embodiment of the present invention provides a method for manufacturing a laminated color-changing glass. The preparation method of the laminated color-changing glass comprises the following steps:
s1, respectively preparing first coated glass, second coated glass and liquid electrolyte;
s2, combining the first coated glass and the second coated glass to form a glass interlayer;
s3, injecting the liquid electrolyte into the glass interlayer to serve as an ion conductor layer;
and S4, carrying out molding treatment on the glass interlayer containing the ion conductor layer to obtain the laminated color-changing glass.
Wherein the liquid electrolyte comprises a lithium-containing compound, an organic solvent and a high-molecular polymer, and the organic solvent is used for dissolving the high-molecular polymer.
The embodiment adopts the liquid electrolyte mixed by the lithium-containing compound, the high-molecular polymer and the organic solvent as the ion conductor layer, which not only ensures higher ion mobility and chemical stability and thermal stability of the electrolyte, but also greatly reduces the production cost because the electrolyte is liquid, the production process is simpler, and the curing agent is not required to be added.
Referring to fig. 2, in particular, the preparing the first coated glass and the second coated glass in step S1 in one embodiment of the present invention specifically includes:
s11, providing a first glass substrate and a second glass substrate;
s12, laying a first conductive layer on the first glass substrate, and laying a main color-changing layer on the first conductive layer to obtain the first coated glass;
And S13, laying a second conductive layer on the second glass substrate, and laying an auxiliary color-changing layer on the second conductive layer to obtain the second coated glass.
Step S3 specifically includes injecting the liquid electrolyte between the main color-changing layer and the auxiliary color-changing layer of the glass interlayer as the ion conductor layer.
Referring to fig. 3, a schematic view of a glass interlayer 101 including an ion conductor layer 30 during the manufacturing process according to an embodiment of the present invention is shown. Including a first coated glass 10, a second coated glass 20, and an ion conductor layer 30. In step S1, a first coated glass 10 is prepared by sequentially laying a first conductive layer 12 and a main color-changing layer 13 on the first glass substrate 11 provided in step S11. The second coated glass 20 is prepared by sequentially laying a second conductive layer 22 and an auxiliary color-changing layer 23 on the second glass substrate 21 provided in step S11. In step S2, the first coated glass 10 and the second coated glass 20 are laminated to form a glass interlayer 101, and in step S3, a liquid electrolyte is injected between the main color change layer 13 and the auxiliary color change layer 23 as the ion conductor layer 30, to obtain the glass interlayer 101 including the ion conductor layer 30. Before the first coated glass 10 and the second coated glass 20 are prepared, for example, the first glass substrate 11 and the second glass substrate 21 are cleaned and heated, and may be pretreated according to actual process requirements in the preparation process, which is not described in detail in this embodiment.
The first glass substrate 10 and the second glass substrate 20 may be float glass, ultra-white glass, high-alumina glass, medium-alumina glass, various-color glass (such as gray glass, green glass, lake blue glass, etc.), PET (Polyethylene terephthalate ) film material, etc.
Further, in one embodiment of the present invention, the step S12 of applying the first conductive layer on the first glass substrate specifically includes applying the first conductive layer to the first glass substrate by using one or a combination of at least two of a semiconductor oxide material, a metal material, or an organic conductive material as a raw material. The semiconductor oxide material is specifically one or a combination of at least two of FTO (fluorine doped tin oxide), ITO (indium tin oxide), IGZO (indium gallium zinc oxide), AZO (aluminum zinc oxide) and the like, the metal material is specifically one or a combination of at least two of Ag (silver), au (gold), cu (copper), al (aluminum) and the like, and the organic conductive material is specifically one or a combination of at least two of polyacetylene (polyethyne), polypyrrole (polypyrrole, PPy), polyaniline (polyaniline, PANI), polythiophene (Polythiophene) and the like. In step S13, laying a second conductive layer on the second glass substrate specifically comprises using one or a combination of at least two of a semiconductor oxide material, a metal material or an organic conductive material as a raw material, and laying the second conductive layer on the second glass substrate. Here, in actual production, the material of the first conductive layer and the material of the second conductive layer are generally the same, but may also be different, which is not limited in this embodiment. The combination of at least two of the types mentioned herein may be, for example, a combination of two such as AZO and GZO, or a combination of three such as FTO, ITO, GZO, or even more, etc. In this embodiment and the above embodiments, the deposition may be performed by using a magnetron sputtering technique to deposit the raw material on the first glass substrate or the second glass substrate, or may be performed by using a pre-prepared conductive film layer to plate the raw material on the first glass substrate or the second glass substrate, which is not limited in this embodiment.
Further, in one embodiment of the present invention, in step S12, applying a primary color-changing layer on the first conductive layer includes applying the primary color-changing layer to the first conductive layer using one or a combination of at least two oxides of W, mo, nb, ti, ta as a raw material. Wherein the at least two oxides in combination are, for example, the oxides of any two of W, mo, nb, ti, ta in combination, such as WMoOx、WNbOx, or the oxides of any three in combination, such as WMoTiOx、WNbTaOx, or even more in combination. The stoichiometric ratio of the oxide may be sufficient oxygen or may be a stoichiometric ratio of less than oxygen. As described above, the deposition may be by using a magnetron sputtering technique to deposit the raw material on the first conductive layer, or may be by using other methods, which is not limited in this embodiment.
Further, in one embodiment of the present invention, step S13, the step of applying an auxiliary color-changing layer on the second conductive layer includes applying the auxiliary color-changing layer onto the second conductive layer by using one or at least two combined oxides of Ni, V, co, ir, fe, mn as a raw material. As described above, the combination of at least two oxides is, for example, ni, V, co, ir, fe, mn, the oxide of any two combinations is, for example, niVOx、NiCoOx、NiIrOx、NiFeOx, or the combination of three or even more. The stoichiometric ratio of the oxide may be sufficient oxygen or may be a stoichiometric ratio of less than oxygen. As described above, the deposition may be by using a magnetron sputtering technique to deposit the raw material on the second conductive layer, or may be by using other methods, which is not limited in this embodiment.
Further, in one embodiment of the present invention, the lithium-containing compound in the liquid electrolyte may be one or a combination of at least two of LiAsF6 (lithium hexafluoroarsenate), liPF6 (lithium hexafluorophosphate), liBF4 (lithium tetrafluoroborate), CF3LiO3 S (lithium trifluoromethanesulfonate), and LiClO4 (lithium perchlorate).
Further, in one embodiment of the present invention, the high molecular polymer in the liquid electrolyte may be one or a combination of at least two of polypropylene carbonate (Poly (propylene carbonate)), polyaniline, polyethylene oxide (Poly (ethylene oxide), PEO), polyacrylonitrile (Poly (acrylonitrile), PAN), polyphenylene oxide (Polyphenylene Oxide, PPO), polyvinylidene fluoride (Poly (vinylidene fluoride), PVDF), polyvinylidene fluoride-hexafluoropropylene (Poly (VINYLIDENE FLUORIDE-co-hexafluoroopylene), PVDF-HFP), polymethyl methacrylate (Poly (methyl methacrylate), PMMA), polyvinyl chloride (Poly (vinyl chloride), PVC), and polyacrylonitrile-methyl acrylate copolymer (Poly (acryl-co-METHYL ACRYLATE)).
Further, in one embodiment of the present invention, the organic solvent in the liquid electrolyte may be one or a combination of at least two of Propylene Carbonate (PC), ethylene Carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), methyl formate, methyl acrylate, methyl butyrate, and ethyl acetate.
Further, in one embodiment of the present invention, the shaping process in step S4 further includes heating the glass interlayer containing the ion conductor layer, for example, to form a first transition layer between the main color-changing layer and the ion conductor layer, and a second transition layer between the auxiliary color-changing layer and the ion conductor layer.
Wherein the first transition layer is, for example, a LiWO salt, tungsten oxide or the like generated by self-chemical reaction of Li in the ion conductor layer and W or the like in the main color-changing layer. The second transition layer is, for example, a LiNiO salt or the like generated by self-chemical reaction of Li in the ion conductor layer with Ni or the like in the auxiliary color-change layer. In the embodiment, by forming the first transition layer and the second transition layer, the movement of Li ions in the main color-changing layer is accelerated, and the reaction speed of the laminated color-changing glass is accelerated.
Referring to fig. 4, a laminated color-changing glass 100 obtained by the method for manufacturing a laminated color-changing glass according to an embodiment of the present invention is shown, and referring to fig. 4, the laminated color-changing glass 100 includes a first glass substrate 11, a first conductive layer 12, a main color-changing layer 13, a first transition layer 41, an ion conductor layer 30, a second transition layer 42, an auxiliary color-changing layer 23, a second conductive layer 22, and a second glass substrate 21, which are sequentially arranged. The components of the materials of each layer may be referred to the materials mentioned in the foregoing embodiments, and will not be described in detail in this embodiment. Of course, the molding process in step S4 is not limited to the heating process of the present embodiment, and may be selected according to actual production requirements, for example, edge sealing, vacuuming, autoclave feeding, and the like are also required.
The preparation method of the laminated glass disclosed by the embodiment of the invention has the beneficial effects that the possible problems of the periodic injection and extraction of lithium ions into and from the color-changing layer can be solved, so that the laminated color-changing glass has the advantages of long service life, good stability and the like.
It should be noted that the above-mentioned embodiments are merely for illustrating the technical solution of the present invention, and not for limiting the same, and although the present invention has been described in detail with reference to the above-mentioned embodiments, it should be understood by those skilled in the art that the technical solution described in the above-mentioned embodiments may be modified or some technical features may be equivalently replaced, and these modifications or substitutions do not make the essence of the corresponding technical solution deviate from the spirit and scope of the technical solution of the embodiments of the present invention.