Chromophore having down-conversion capability, encapsulant film, glass, and photovoltaic module
Patent Information
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- CHANGZHOU SVECK PHOTOVOLTAIC NEW MATERIAL CO LTD
- Filing Date
- 2026-01-05
- Publication Date
- 2026-07-02
Smart Images
Figure CN2026070440_02072026_PF_FP_ABST
Abstract
Description
Chromogens with down-conversion capability, encapsulating films, glass and photovoltaic modules Technical Field
[0001] This invention belongs to the field of photovoltaic module technology, specifically relating to a chromophore with down-conversion capability, an encapsulating film, glass, and a photovoltaic module. Background Technology
[0002] In photovoltaic power generation modules, solar cells can utilize sunlight wavelengths between 400 nm and 1100 nm; ultraviolet light with wavelengths between 220 nm and 400 nm cannot be utilized by solar cells and is harmful to them.
[0003] Introducing a light-converting agent into the encapsulating film converts harmful ultraviolet rays with low quantum efficiency in the solar spectrum into beneficial visible light with high quantum efficiency. This not only avoids damage to photovoltaic modules from ultraviolet rays but also improves photoelectric conversion efficiency.
[0004] However, existing photovoltaic modules exhibit a decline in light conversion capability and UV resistance after prolonged use. This leads to a higher yellowing index at the cell gaps compared to other areas, resulting in reduced module power. This is because existing light conversion agents—organic phosphors, rare-earth organic complexes, rare-earth inorganic compounds, CdSe quantum dots, or perovskite quantum dots—exist in a free state within the encapsulant system. When localized temperature changes occur within the module or when a concentration difference exists within the encapsulant, these agents migrate within the system. In photovoltaic modules, light conversion agents are typically added only to the front encapsulant film, while the back encapsulant film remains untouched. Due to the concentration difference, the agents in the front encapsulant film diffuse continuously to the back through the cell gaps, causing a decrease in the concentration of light conversion agents in the front encapsulant film. This reduces the module's light conversion capability, leading to yellowing of the surface under UV light, particularly at the cell gaps. Yellowing reduces light transmittance in these areas, causing hot spot effects. The increased temperature further promotes agent migration, creating a vicious cycle.
[0005] Therefore, overcoming the migration defects of light-converting agents caused by temperature differences and concentration is a technical problem that urgently needs to be solved in this field.
[0006] It should be noted that the information disclosed in this background section is only for understanding the background technology of the present application concept, and therefore, the above description is not considered to constitute prior art information. Summary of the Invention
[0007] This disclosure provides at least one chromophore with downconversion capability, an encapsulating film, glass, and a photovoltaic module.
[0008] In a first aspect, embodiments of this disclosure provide a chromophore with downconversion capability, the structural formula of which is as follows:
[0009] I-1; and / or
[0010] Ⅰ-2
[0011] Where n is any integer from 0 to 100; E 0 Including any one of alkynyl, alkenyl, silane, silane-phenyl, and silylenyl; E 2 Selected from optionally substituted silanes, silenes, alkylenes, alkenylenes, silanes, heteroarylenes, ketones, and esters; G x Independently selected from optionally substituted alkylene, silene, optionally substituted olefinyl, silyleneyl, alkenyl, optionally substituted alkenyl, optionally substituted aryl, optionally substituted silanearyl; and said A 1 A 2 Each is independently selected from the substituted aryl group, the substituted heteroaryl group; or the A group. 1 A 2 Each is independently selected from substituted silane heterocyclic groups, silane benzo[a]heterocyclic compound groups, or optionally substituted silane groups.
[0012] In one alternative implementation, E 0 Selected from C1-C8 alkenyl, alkynyl, silane, silane-phenyl, and C1-C8 silylene.
[0013] In one alternative embodiment, the heteroaryl group is selected from benzothiazolyl, benzoxazinyl, quinazolinyl, quinolinyl, isoquinolinyl, quinoxalinyl, pyridyl, pyrroleyl, purazolyl, indolyl, azinyl, pyrimidinyl, pyrazinyl, 2-pyridin-5-yl, furanyl, dibenzofuran-4-yl, benzofuran, dihydrophenodioxaneyl, benzothiopheneyl, and dibenzothiopheneyl.
[0014] In one alternative embodiment, the substituents of the substituted aryl and heteroaryl groups are selected from siloxanes, aminosilanes, silane heterocyclic groups, and silane hybrid benzocycloides.
[0015] In one alternative implementation, A 1 A 2 Each is independently selected from substituted benzofuranyl, substituted furanyl, dihydrothiophene dioxaneyl, substituted benzothiopheneyl, and substituted dibenzothiopheneyl.
[0016] In one alternative implementation, E 0It is selected from C1-C8 alkenyl, silane, silane-phenyl, and C1-C8 silyl alkenyl; and A 1 A 2 Each is independently selected from the substituted silanearyl group.
[0017] In an optional embodiment, the substitution in the substituted aryl group or the substituted heteroaryl group refers to one or more individual and independent functional groups selected from organosilicon derivatives including C1-C6 silyl, C1-C6 silenyl, C1-C6 silynyl, C3-C7 silanecycloalkyl, C2-C7 silanecycloalkenyl, silanebenzylheterocyclic, halosilane, silanol, silyl ether, siloxene, silyl ester, silaldehyde, benzylsilane, arylsilane, acylsilane, halosiloxane, silicone, silanecarbamate, aminosilane, cyanosilicon, mercaptosilane, nitrosilane, glycylsilane, thiosilane, hydrazinosilane, and ureosilane.
[0018] In one optional embodiment, the silane heterocyclic compound group includes, but is not limited to, silane four-membered ring compound group, silane five-membered ring compound group, and silane phenyl group; the silane benzo[a] heterocyclic compound group includes, but is not limited to, silane four-membered ring benzo[a] benzene compound group, silane five-membered ring benzo[a] benzene compound group, and silane benzo[a] benzene compound group; wherein the silane four-membered ring compound group includes, but is not limited to, silane butene group and silane butyl group; the silane five-membered ring compound group includes, but is not limited to, silane pentyl group and silane pentadiene group.
[0019] In an optional embodiment, the substitution in the substituted silane heterocyclic group and the silane-substituted benzo[a]heterocyclic compound group refers to one or more individual and independent organosilicon derivative functional groups selected from C1-C6 silane, C1-C6 silenyl, C1-C6 silynyl, C3-C7 silane heterocyclic alkyl, C2-C7 silane heterocyclic alkenyl, silane-substituted benzo[a]heterocyclic, halosilane, silanol, silyl ether, siloxene, silyl ester, silaldehyde, benzylsilane, arylsilane, acylsilane, halosiloxane, silicone, silanecarbamate, aminosilane, cyanosilicon, mercaptosilane, nitrosilane, glycylsilane, thiosilane, hydrazinosilane, and ureosilane.
[0020] In one alternative embodiment, the substituents of the substituted siloxane group and the silane-substituted benzocyclone compound group are selected from siloxane, aminosilane, siloxane group and silane-hybridized benzocyclone group.
[0021] In one alternative implementation, A 1 A 2 Each is independently a siloxane or aminosilane, optionally substituted with heterosilylphenyl.
[0022] In one alternative implementation, E 0It is selected from C1-C8 alkenyl, silane, silane-phenyl, and C1-C8 silyl alkenyl; and A 1 A 2 Each is independently selected from optionally substituted arylsilyl or optionally substituted silyl.
[0023] In one alternative implementation, its structure is as follows:
[0024] II-1; and / or
[0025] II-2;
[0026] Where n is any integer from 0 to 100; E 0 It is selected from alkynyl, alkenyl, silane, silane-phenyl, and silylene; E 1 Selected from optionally substituted silanes, silenes, alkylenes, alkenylenes, silanes, heteroarylenes, ketones, and esters; G x Independently selected from optionally substituted alkylene, optionally substituted alkylene, alkylene-silylene, alkylene-silylene, alkenyl, optionally substituted alkylene-silylene, optionally substituted arylene, optionally substituted silane-arylene; R 1 The substituted functional group is independently selected from any substituted siloxane, aminosilane, heterosilylphenyl, C1-C6 alkoxy, aryloxy, and amino groups; wherein the substituted and the substituted group refers to one or more individual and independent functional groups selected from organosilicon derivatives including C1-C6 silane, C1-C6 silene, C1-C6 silynyl, C3-C7 silane-heterocyclic, C2-C7 silane-heterocyclic, halosilane, silanol, silyl ether, siloxene, silyl ester, silaldehyde, benzylsilane, arylsilane, acylsilane, halosiloxane, silicone, silanecarbamate, aminosilane, cyanosilicon, mercaptosilane, nitrosilane, glycylsilane, thiosilane, hydrazinosilane, and ureosilane.
[0027] Secondly, embodiments of this disclosure also provide an encapsulating film with downconversion capability, comprising: at least one luminescent dye prepared from a chromophore with downconversion capability as described above, and an organic polymer material.
[0028] In one optional embodiment, the thickness of the encapsulating film is 10-1000 μm; and the mass percentage of the chromophore with downconversion capability is 0.01-2 wt%.
[0029] In one alternative embodiment, the organic polymer material includes any one or more combinations of thermoplastic polyolefins, polyvinyl butyral, polyolefin elastomers, polyurethanes, thermoplastic polyurethanes, polyacrylates, ethylene vinyl acetate copolymers, organosilicones, and ionomers.
[0030] In one optional embodiment, the encapsulating film comprises the following components by weight: 100 parts organic polymer material, 0.01-2 parts chromophore, 0.01-1.1 parts light stabilizer, 0.1-2 parts crosslinking agent, 0.1-2 parts co-crosslinking agent, 0.01-1 parts antioxidant, and 0.1-1.2 parts silane coupling agent.
[0031] Thirdly, embodiments of this disclosure also provide a glass with downconversion capability, comprising: at least one surface containing a luminescent dye prepared from a chromophore with downconversion capability as described above.
[0032] Fourthly, embodiments of this disclosure also provide a photovoltaic module, including: an encapsulating film having down-conversion capability as described above and / or glass having down-conversion capability as described above.
[0033] In one optional embodiment, the photovoltaic module is a single-glass module, comprising, from top to bottom, glass, a first encapsulating film, a solar cell, a second encapsulating film, and a backsheet; wherein the first encapsulating film includes a luminescent dye made from a chromophore with down-conversion capability as described above, and / or the glass includes a luminescent dye made from a chromophore with down-conversion capability as described above.
[0034] In one optional embodiment, the photovoltaic module is a double-glass module, comprising, from top to bottom, a first glass, a first encapsulating film, a solar cell, a second encapsulating film, and a second glass; wherein the first encapsulating film includes a luminescent dye made from a chromophore with down-conversion capability as described above, and / or the first glass includes a luminescent dye made from a chromophore with down-conversion capability as described above.
[0035] The beneficial effects of this invention are that the chromophores, encapsulating films, glass, and photovoltaic modules with downconversion capabilities are synthesized by synthesizing chromophores with unsaturated double bonds, triple bonds, and silanes. With the cooperation of crosslinking agents, they can chemically bond with the unsaturated bonds in the encapsulating film polymer or encapsulating glass, thus building a stable, high-temperature resistant, and chemically resistant network structure. This avoids the migration of chromophores due to the influence of temperature and concentration, and effectively improves the light conversion efficiency of photovoltaic modules.
[0036] Other features and advantages of the invention will be set forth in the following description, and will be apparent in part from the description, or may be learned by practicing the invention. The objects and other advantages of the invention are realized and obtained through the structures particularly pointed out in the description and the drawings.
[0037] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, preferred embodiments are described below in detail with reference to the accompanying drawings. Attached Figure Description
[0038] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.
[0039] Figure 1 is a schematic diagram of the synthesis route of chromophores in some embodiments of this disclosure;
[0040] Figure 2 is a diagram of the blue fluorescent band at the ultraviolet lamp irradiation point at the back gap of the photovoltaic module provided in Embodiment 1 of this disclosure under the initial condition;
[0041] Figure 3 shows the blue fluorescent band at the ultraviolet lamp irradiation point of the back gap of the photovoltaic module of Embodiment 1 provided in this disclosure after 12 months outdoors;
[0042] Figure 4 shows the blue fluorescent band at the ultraviolet lamp irradiation point of the back gap of the photovoltaic module provided in Comparative Example 2 after 12 months outdoors, according to an embodiment of this disclosure. Detailed Implementation
[0043] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0044] As used herein, the phrases “in one embodiment,” “according to one embodiment,” “in some embodiments,” etc., generally refer to the fact that a particular feature, structure, or characteristic following the phrase can be included in at least one embodiment of this disclosure. Therefore, a particular feature, structure, or characteristic can be included in more than one embodiment of this disclosure, such that these phrases do not necessarily refer to the same embodiment. As used herein, the terms “example,” “exemplary,” etc., are used to “serve as an example, instance, or illustration.” Any implementation, aspect, or design described herein as “example” or “exemplary” is not necessarily to be construed as preferred or superior to other implementations, aspects, or designs. Rather, the use of the terms “example,” “exemplary,” etc., is intended to present concepts in a specific manner.
[0045] In this document, exemplary embodiments of the present disclosure will be described in more detail with reference to the accompanying drawings. As used herein, expressions such as “at least one of…” modify the entire list of elements when following a list of elements, rather than individual elements in the list. For example, the expression “at least one of a, b, and c” should be understood to include only a, only b, only c, both a and b, both a and c, both b and c, or all of a, b, and c.
[0046] The terminology used herein is for the purpose of describing specific exemplary configurations only and is not intended to be limiting. As used herein, the singular articles “a,” “an,” and “the” may also be intended to include plural forms unless otherwise clearly stated herein. The terms “comprising,” “including,” and “having” are inclusive and thus specify the presence of features, steps, operations, elements, and / or components, but do not preclude the presence or addition of one or more other features, steps, operations, elements, components, and / or combinations thereof. The method steps, processes, and operations described herein should not be construed as requiring them to be performed in the specific order discussed or shown, unless specifically identified as such. Additional or alternative steps may be employed.
[0047] The term "silicon heterocyclic group" as used in this article refers to a four-, five-, or six-membered ring in which one or more ring atoms are the same or different Si, O, S, N, or Se atoms, and at least one heteroatom is a Si atom.
[0048] The terms “C1-C6 silyl group, C1-C6 silene group, C1-C6 silynyl group, C3-C7 silane-heterocyclic alkyl group, C2-C7 silane-heterocyclic alkyl group, halosilane, silanol, silyl ether group, siloxene, silyl ester, silaldehyde, benzylsilane, arylsilane, acylsilane, halosiloxane, silicone, silanecarbamate, aminosilane, cyanosilicon, mercaptosilane, nitrosilane, glycylsilane, thiosilane, hydrazylsilane, ureosilane, etc.” mentioned in this article are all silicon derivative groups containing one or more silicon atoms.
[0049] It should be noted that similar labels and letters in the following figures indicate similar items. Therefore, once an item is defined in one figure, it does not need to be further defined and explained in subsequent figures.
[0050] The following detailed description of some embodiments of the present invention is provided in conjunction with the accompanying drawings. Unless otherwise specified, the following embodiments and features can be combined with each other.
[0051] Some specific solutions are shown below:
[0052] Ⅰ-1 Ⅰ-2
[0053] Specifically, A1 and A2 are Si or organosilicon derivative groups containing Si atoms, and G... x It is a linker for benzotriazole and can be an organosilicon derivative group.
[0054] In some specific implementations, at least one of A1 and A2 is an organosilicon derivative group containing Si atoms, and G x It can be an organosilicon derivative group containing Si atoms.
[0055] Specifically, in I-1 and I-2, where n is an integer from 0 to 100, E 0 and E x Each group is independently selected from optionally substituted silyl groups, silane heterocyclic groups, silane benzocyclic compound groups, alkenyl groups, heteroalkyl groups, aryl groups, heteroaryl groups, amino groups, amide groups, cyclic amide groups, cyclic imino groups, alkoxy groups, carboxyl groups, and carbonyl groups.
[0056] In some specific implementation schemes, n is 0-10, 0-20, or 0-30.
[0057] In some specific implementation schemes, n is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9.
[0058] In some specific implementation schemes, E 0 and E x Each is independently selected from optionally substituted heteroaryl, cyclic imide, C 1-8 Alkenyl, wherein the substituent of the optionally substituted heteroaryl group is selected from silyl, arylsilyl, and halosilyl groups; the optional substituted aryl group is -NR. 4 -C(=0)R 4 Or optionally substituted cyclic iminosilyl groups, wherein R 4 Independently selected from silyl, silylene, silane heterocyclic, silanized benzocyclic compound groups, silylene, silylene, silyloxy, silane-aryl, and simultaneously, two R... 4 Not both hydrogen and R 4 -R 4 They can be connected to form a ring.
[0059] Specifically, in equations I-1 and I-2, E 2 Selected from optionally substituted silyl, silylene, alkylene, alkenyl, oxy-, silane-aryl, heteroaryl, ketone, and ester.
[0060] In some specific implementation schemes, E 2 Selected from optionally substituted silylene, silane-aryl, and siloxane.
[0061] Specifically, in equations I-1 and I-2, A 1 and A2 Each is independently selected from hydrogen, optionally substituted siloxanes, arylsilanes, silanes, silane heterocyclic groups, silane-benzocyclohexane groups, aminosilanes, and amide silanes, wherein A 1 and A 2 Both are not hydrogen at the same time.
[0062] In some specific implementation plans, A 1 and A 2 Each is independently selected from hydrogen, optionally substituted silane heterocyclic groups, silane benzocyclic compound groups, and aminosilanes, wherein A 1 and A 2 They are not both hydrogen.
[0063] In some specific implementation plans, A 1 and A 2 Each is a substituted aryl group, and the substituted group is selected from silyl, silene, silynyl, and siloxane groups.
[0064] In some specific implementation plans, A 1 and A 2 Each is a phenyl group that has been substituted with either a siloxy group or an aminosilyl group.
[0065] In some specific implementation plans, A 1 and A 2 Each of the following is independently selected from hydrogen, substituted benzofuranyl, substituted thiophenyl, substituted furanyl, substituted benzothiophenyl, and substituted dibenzothiophenyl, and is A. 1 and A 2 The substituents are not all hydrogen; the substituents in the substituted group are selected from C1-C6 silane groups, C1-C6 silene groups, C1-C6 silynyl groups, C3-C7 silanecycloalkyl groups, and C2-C7 silanecycloolefin groups.
[0066] Specifically, in equations I-1 and I-2, G x Independently selected from optionally substituted silylene, optionally substituted alkylene, alkylene silylene, alkylene silylene, alkylene, optionally substituted alkylene, optionally substituted arylene, optionally substituted silane arylene.
[0067] In some specific implementation schemes, G x Independently selected from optionally substituted arylene or optionally substituted silanearylene.
[0068] Some specific solutions are shown below.
[0069] II-1
[0070] II-2
[0071] Specifically, in Equations II-1 and II-2, n is an integer from 0 to 100, and in some specific implementations, n is 0-10, 0-20, or 0-30.
[0072] In some specific implementation schemes, n is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9.
[0073] Specifically, in equations II-1 and II-2, E 0 and E x Each group is independently selected from optionally substituted silyl groups, silane heterocyclic groups, silane benzocyclic compound groups, alkenyl groups, heteroalkyl groups, aryl groups, heteroaryl groups, amino groups, amide groups, cyclic amide groups, cyclic imino groups, alkoxy groups, carboxyl groups, and carbonyl groups.
[0074] In some specific implementation schemes, E 0 and E x Each of these is a silyl group or a partially substituted silyl group: -NRR", -OR, -COOR, -COR, -CONHR, -ONRR", halosilane, -SiN, where R is C1-C. 20 Silyl group, where "R" is hydrogen or C1-C 20 Silyl group.
[0075] In some specific solutions, E 0 and E x Each is independent of the others, namely C1-C. 50 Silyl or C1-C 30 Halosilanes, C1-C 20 Silyl, aryl C1-C 20 Silyl group.
[0076] Specifically, in equations II-1 and II-2, each R 1 Each is independently selected from optionally substituted siloxanes, siloxanes, arylsilanes, silanes, aminosilanes, and amide silanes.
[0077] In some specific implementation schemes, R 1 It is a silane-phenyl ring.
[0078] In some specific implementation schemes, R 1 It is an organosilicon derivative containing siloxane alkyl groups.
[0079] In some specific embodiments, arylsilanes are defined as Ar-Si-O or O-SiR-OAr, where R is an alkane, silane, substituted alkane, silane, aryl, or silane-aryl. Ar can be any substituted aryl or silane-aryl.
[0080] In some specific solutions, R 1 It is an amide silane.
[0081] Specifically, in equations II-1 and II-2, E 1 Selected from optionally substituted silanes, silenes, alkylenes, alkenylenes, oxy-oxides, silanes, heteroarylenes, ketones, and esters.
[0082] Specifically, in equations II-1 and II-2, G x Independently selected from optionally substituted alkylene, optionally substituted alkylene silylene, alkylene silylene, alkenyl, optionally substituted alkylene silylene, optionally substituted arylene, optionally substituted silane arylene.
[0083] This paper discloses a photovoltaic encapsulating film with down-conversion capability and an organosilicon glass with down-conversion capability; it can convert harmful ultraviolet light with low quantum efficiency in the solar spectrum into beneficial visible light with high quantum efficiency, while maximizing the adhesion and environmental adaptability of the photovoltaic encapsulating film. The encapsulating film is characterized by comprising an organic polymer matrix and at least one luminescent dye with a chromophore disclosed herein.
[0084] Specifically, the organic polymer matrix of the encapsulating film includes thermoplastic polyolefins, polyvinyl butyral, polyolefin elastomers, polyurethanes, thermoplastic polyurethanes, polyacrylates, ethylene vinyl acetate copolymers, silicones, ionomers, and combinations thereof.
[0085] Specifically, the encapsulating film has a film structure consisting of one or more co-extruded composite structures composed of one or more organic polymer matrices. Its thickness is 10–1000 μm; its chromophore content is 0.01–2 wt%, and because the chromophores contain unsaturated bonds, they can cross-link with the organic polymer matrix to form a stable network structure.
[0086] Specifically, the encapsulating film comprises the following components in parts by weight:
[0087] The organic polymer matrix is 100 parts by weight.
[0088] The chromophore is present in parts by weight of 0.01 to 2 parts, for example, 0.01 parts, 0.02 parts, 0.03 parts, 0.04 parts, 0.05 parts, 0.06 parts, 0.07 parts, 0.08 parts, 0.09 parts, 1.0 parts, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, and 2.0 parts.
[0089] The light stabilizer is 0.01 to 1.1 parts, for example, 0.01 parts, 0.02 parts, 0.03 parts, 0.04 parts, 0.05 parts, 0.06 parts, 0.07 parts, 0.08 parts, 0.09 parts, 1.0 parts, or 1.1 parts.
[0090] The crosslinking agent is 0.1 to 2 parts, for example, 0.1 parts, 0.2 parts, 0.1 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts, 1.5 parts, or 2.0 parts.
[0091] The crosslinking agent is 0.1 to 2 parts, for example, 0.1 parts, 0.2 parts, 0.1 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts, 1.5 parts, or 2.0 parts.
[0092] Antioxidant 0.01 to 1 part, for example 0.01 parts, 0.02 parts, 0.03 parts, 0.04 parts, 0.05 parts, 0.06 parts, 0.07 parts, 0.08 parts, 0.09 parts, 1.0 parts.
[0093] The silane coupling agent is used in amounts of 0.1 to 1.2 parts, for example, 0.1 parts, 0.2 parts, 0.1 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts, and 1.2 parts.
[0094] An organosilicon glass with downconversion capability, the organosilicon glass containing at least one luminescent dye with a chromophore disclosed herein. The silane in the chromophore undergoes a coupling reaction with the glass to form a stable chemically bonded light-conversion layer structure.
[0095] A photovoltaic module includes two encapsulation forms: single-glass and double-glass. In a single-glass module, from top to bottom, the components are glass, encapsulation film 1, solar cells, encapsulation film 2, and a backsheet. In a double-glass module, from top to bottom, the components are glass, encapsulation film 1, solar cells, encapsulation film 2, and glass 2. Encapsulation film 1 is a down-conversion encapsulation film containing the chromophores described in this invention. After lamination, the chromophores undergo a cross-linking reaction with the organic polymer matrix to form a stable network structure.
[0096] A photovoltaic module is characterized in that the encapsulating film used in the photovoltaic module contains at least one luminescent dye of the chromophore disclosed herein, and the encapsulating glass used is ordinary glass or an organosilicon glass with downconversion capability containing at least one luminescent dye of the chromophore disclosed herein; after the photovoltaic module is laminated, the unsaturated double and triple bonds in the chromophore crosslink with the unsaturated bonds in the organic matrix under the action of a crosslinking agent, thereby constructing a stable, high-temperature resistant, and chemically resistant network structure.
[0097] Please refer to Figure 1. As shown in Figure 1, the specific synthesis methods and detailed steps for some chromophores are as follows:
[0098] Preparation of compound 2:
[0099] Dissolve 1,2-diaminebenzene (compound 1) (10 g, 70.0 mmol) in acetic acid (9 mL, 140 mmol), add water (360 mL) and heat; cool the mixture and add NaNO2 (5 g, 77 mmol) and water (150 mL); then stir the mixture at room temperature for 1 hour, cool when it turns dark green, filter the precipitate, dry it, recrystallize it with water to give solid benzo[d][1,2,3]triazole (8 g) (compound 2).
[0100] Preparation of compound 3:
[0101] Compound 2 (8.0 g, 51.2 mmol) was dissolved in 100 mL of methanol. Potassium tert-butoxide (14.4 g, 128.8 mmol) and 6-bromo-1-hexene (16.59 g, 103.2 mmol) were added to the solution, and the mixture was stirred at 65 °C for 24 hours. The mixture was cooled to room temperature, water was added, and the organic layer was extracted with ethyl acetate. The organic layer was dried on MgSO4 and concentrated under reduced pressure. Hexane and ethyl acetate were prepared as an eluent at a volume ratio of 50:1, and the product was purified by silica gel column chromatography to give 2-(hex-5-en-1-yl)-2H-benzo[d][1,2,3]triazole (compound 3) (5.3 g).
[0102] Preparation of compound 4:
[0103] Compound 3 (6.6 g, 27.80 mmol) was dissolved in 80 mL of toluene, and a small amount of Karstedt catalyst (2.42 mL, 0.005 equip) and 1,1,1,3,5,5,5-heptamethyltrisiloxane (7.11 g, 31.98 mmol) were added to the solution. The mixture was stirred at 50 °C for 24 h, concentrated, and toluene was removed under vacuum to obtain an oil mixture. The oil mixture was purified by silica gel column chromatography using a 50:1 volume ratio of hexane and ethyl acetate as an eluent to give 2-(6-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)hexyl)-2H-benzo[d][1,2,3]triazole (compound 4) (3.2 g).
[0104] Preparation of compound 5 (chromophore 1):
[0105] Under a nitrogen atmosphere at -78 °C, lithium diisopropylamide (LDA) (2.0 M, 14.50 mL, 29.04 mmol) was added dropwise to a 50 mL solution of anhydrous THF (4.5 g, 9.68 mmol) of compound 4. Then, trimethylsilyl chloride (3.15 g, 29.03 mmol) was added dropwise at -78 °C, and the mixture was stirred for 5 h and quenched with 10 mL of saturated NH4Cl solution. The reaction was heated to room temperature, and saturated NH4Cl solution was added stepwise, followed by the addition of a mixture of CHCl3 to extract the organic layer, which was then washed twice with water. The organic layer was dried on MgSO4 and concentrated under reduced pressure. The product was purified by silica gel column chromatography by preparing an eluent of n-hexane and ethyl acetate in a volume ratio of 60:1 to obtain 2-(6-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)hexyl)-4,7-bis(trimethylsilyl)-2H-benzo[d][1,2,3]triazole (compound 5, chromophore 1) (2.3 g).
[0106] Preparation of compound 6 (chromophore 2):
[0107] Under a nitrogen atmosphere at -78 °C, lithium diisopropylamide (LDA) (2.0 M, 14.50 mL, 29.04 mmol) was added dropwise to an anhydrous THF (50 mL) solution of compound 3 (5.2 g, 11.18 mmol). Then, trimethylsilyl chloride (3.2 g, 29.07 mmol) was added dropwise at -78 °C, the mixture was stirred for 5 h, and quenched with 10 mL of saturated NH4Cl solution. The reaction was heated to room temperature, and saturated NH4Cl solution was added stepwise, followed by the addition of a mixture of CHCl3 to extract the organic layer, which was then washed twice with water. The organic layer was dried over anhydrous MgSO4 and concentrated under reduced pressure. The product was purified by silica gel column chromatography by preparing 2-(hex-5-en-1-yl)-4,7-bis(trimethylsilyl)-2H-benzo[d][1,2,3]triazole (compound 6, chromophore 2) by mixing hexane and ethyl acetate in a volume ratio of 60:1.
[0108] Preparation of compound 7:
[0109] Compound 2 (4.21 g, 22.5 mmol, 1 equip) and anhydrous potassium carbonate (3.78 g, 27 mmol, 1.2 equip) were placed in a 250 mL double-necked round-bottom flask, followed by the addition of N,N-dimethylformamide (100 mL). Then, 1-bromo-2-hexyl-10-decene (7.08 g, 22.5 mmol, 1 equip) was added dropwise, and the mixture was stirred at 150 °C for 12 hours under argon protection. After cooling to room temperature, the mixture was poured into water (300 mL) and extracted several times with dichloromethane. The combined organic phases were washed twice with water and dried over anhydrous MgSO4. After solvent removal by rotary evaporation, the crude product (compound 7) (6.21 g) was purified by silica gel column chromatography (eluent: dichloromethane: petroleum ether = 1:10) to remove the solvent.
[0110] Preparation of compound 8 (chromophore 3):
[0111] Under a nitrogen atmosphere at -78°C, lithium diisopropylamide (LDA) (14.7 mL, 29.4 mmol, 2 M, 2.2 equip) was added dropwise to an anhydrous THF (80 mL) solution of compound 7 (5.47 g, 13.3 mmol, 1 equip). The reaction mixture was stirred at this temperature for 1 hour. Subsequently, an anhydrous THF (20 mL) solution of trimethylchlorosilane (3.45 g, 31.12 mmol, 2.34 equip) was added dropwise to the reaction solution, and the mixture was stirred at this temperature for 3 hours. After 4 days, the mixture was poured into a saturated ammonium chloride solution and extracted with chloroform. The combined organic phases were washed twice with water, dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and the crude product (compound 8, chromophore 3) was purified by silica gel column chromatography (eluent: dichloromethane: petroleum ether = 1:10).
[0112] The following are some specific examples.
[0113] Example 1: Components by weight: 100 parts ethylene-vinyl acetate; 1.5 parts tert-butylperoxide-2-ethylhexyl carbonate as crosslinking agent; 0.3 parts triallyl isocyanurate as co-crosslinking agent; 0.8 parts γ-methacryloyloxypropyltrimethoxysilane as silane coupling agent; 0.5 parts β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate as antioxidant; 0.3 parts bis(2,2,6,6-tetramethylpiperidinyl) sebacate as light stabilizer; 0.3 parts chromophore 1.
[0114] Materials are taken according to the weight composition of the encapsulant film, mixed evenly using an automatic mixer, and then extruded using a screw extruder to prepare a light-converting EVA encapsulant film. The film is then assembled from top to bottom in the following order: glass, light-converting EVA encapsulant film 1, solar cell, ordinary EVA encapsulant film 2, and glass. After lamination, a double-glass module is prepared.
[0115] Example 2: A photovoltaic module was prepared using the same method as in Example 1, except that the downconversion reagent was chromophore 2.
[0116] Components by weight: 100 parts ethylene-vinyl acetate; 1.5 parts tert-butylperoxide-2-ethylhexyl carbonate as crosslinking agent; 0.3 parts triallyl isocyanurate as co-crosslinking agent; 0.8 parts γ-methacryloyloxypropyltrimethoxysilane as silane coupling agent; 0.5 parts β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate as antioxidant; 0.3 parts bis(2,2,6,6-tetramethylpiperidinyl) sebacate as light stabilizer; 0.3 parts chromophore 2.
[0117] Materials are taken according to the weight composition of the encapsulant film, mixed evenly using an automatic mixer, and then extruded using a screw extruder to prepare a light-converting EVA encapsulant film. The film is then assembled from top to bottom in the following order: glass, light-converting EVA encapsulant film 1, solar cell, ordinary EVA encapsulant film 2, and glass. After lamination, a double-glass module is prepared.
[0118] Example 3: Photovoltaic modules were prepared using the same method as in Example 1, except that the downconversion reagent was chromophore 3.
[0119] Components by weight: 100 parts ethylene-vinyl acetate; 1.5 parts tert-butylperoxide-2-ethylhexyl carbonate as crosslinking agent; 0.3 parts triallyl isocyanurate as co-crosslinking agent; 0.8 parts γ-methacryloyloxypropyltrimethoxysilane as silane coupling agent; 0.5 parts β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate as antioxidant; 0.3 parts bis(2,2,6,6-tetramethylpiperidinyl) sebacate as light stabilizer; 0.3 parts chromophore 3.
[0120] Materials are taken according to the weight composition of the encapsulant film, mixed evenly using an automatic mixer, and then extruded using a screw extruder to prepare a light-converting EVA encapsulant film. The film is then assembled from top to bottom in the following order: glass, light-converting EVA encapsulant film 1, solar cell, ordinary EVA encapsulant film 2, and glass. After lamination, a double-glass module is prepared.
[0121] Example 4: A photovoltaic module was prepared using the same method as in Example 1. The difference from Example 1 was that the chromophore 1 in the encapsulation film formulation was 0.2 parts.
[0122] Example 5: A photovoltaic module was prepared using the same method as in Example 2. The difference from Example 2 was that the chromophore 2 in the encapsulation film formulation was 0.2 parts.
[0123] Example 6: A photovoltaic module was prepared using the same method as in Example 3. The difference from Example 3 was that the chromophore 3 in the encapsulation film formulation was 0.2 parts.
[0124] Comparative Example 1: The difference from Example 1 is that it does not contain downconversion reagent.
[0125] Components by weight: 100 parts ethylene-vinyl acetate; 1.5 parts tert-butylperoxide-2-ethylhexyl carbonate as crosslinking agent; 0.3 parts triallyl isocyanurate as co-crosslinking agent; 0.8 parts γ-methacryloyloxypropyltrimethoxysilane as silane coupling agent; 0.5 parts β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate as antioxidant; 0.3 parts bis(2,2,6,6-tetramethylpiperidinyl) sebacate as light stabilizer.
[0126] Materials are taken according to the weight composition of the encapsulant film, mixed evenly using an automatic mixer, and then extruded using a screw extruder to prepare a light-converting EVA encapsulant film. The film is then assembled from top to bottom in the following order: glass, light-converting EVA encapsulant film 1, solar cell, ordinary EVA encapsulant film 2, and glass again. After lamination, a double-glass module is prepared.
[0127] Comparative Example 2: The difference from Example 1 is that the downconversion reagent is not the anti-migration chromophore of this invention.
[0128] Components by weight: 100 parts ethylene-vinyl acetate; 1.5 parts tert-butylperoxide-2-ethylhexyl carbonate as crosslinking agent; 0.3 parts triallyl isocyanurate as co-crosslinking agent; 0.8 parts γ-methacryloyloxypropyltrimethoxysilane as silane coupling agent; 0.5 parts β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate as antioxidant; 0.3 parts bis(2,2,6,6-tetramethylpiperidinyl) sebacate as light stabilizer; 0.3 parts 2-(2-ethylhexyl)-4,7-diphenyl-2H-benzo[D][1,2,3]triazole as downconversion chromophore.
[0129] Materials are taken according to the weight composition of the encapsulant film, mixed evenly using an automatic mixer, and then extruded using a screw extruder to prepare a light-converting EVA encapsulant film. The film is then assembled from top to bottom in the following order: glass, light-converting EVA encapsulant film 1, solar cell, ordinary EVA encapsulant film 2, and glass again. After lamination, a double-glass module is prepared.
[0130] Table 1: Experimental data for examples and comparative examples.
[0131] Example Components Efficiency Decrease (%) after 12 Months of Sun Exposure Yellowing Index after 12 Months of Sun Exposure Comparative Example 1: 3.16, 6.42; Comparative Example 2: 2.28, 3.15; Example 1: 0.65, 1.39; Example 2: 0.54, 1.19; Example 3: 0.58, 1.65; Example 4: 0.87, 1.45; Example 5: 1.31, 3.56; Example 6: 0.79, 2.52
[0132] As shown in Table 1, the photochromic groups with anti-migration properties disclosed herein are added to the EVA film. Since the photochromic groups are organosilicon derivatives with unsaturated bonds, after lamination, the organosilicon forms a three-dimensional network structure. Through the action of a crosslinking agent, the unsaturated double and triple bonds in the photochromic groups crosslink with the unsaturated bonds in the organic matrix, constructing a stable, high-temperature resistant, and chemically resistant network structure. This ensures that the module has stable UV resistance, thereby ensuring that the module has a low efficiency degradation rate and yellowing index.
[0133] Yellowing index is measured using a spectrophotometer. First, the initial yellowness value of the sample is measured. Five points are tested on each sample, and the average value Y1 is taken. After placing it outdoors for 12 months, the yellowness value Y2 is measured. Yellowing index ΔY = Y2 - Y1.
[0134] Backside migration distance of a module: When the backside of a photovoltaic module is irradiated with a UVA 365nm ultraviolet lamp in a dark environment, the backside will emit blue light due to the light conversion reagent. The width of the blue fluorescent band is the backside migration distance of the module.
[0135] Please refer to Figures 2-4. Figure 2 shows the blue fluorescent band at the back gap of the photovoltaic module of Example 1 under UV light irradiation in the initial state. The width of the back fluorescent band under UV light irradiation in Example 1 and Comparative Example 2 is similar in the initial state. Figure 3 shows the blue fluorescent band at the back gap of Example 1 under UV light irradiation after 12 months outdoors. Figure 4 shows the blue fluorescent band at the back gap of Comparative Example 2 under UV light irradiation after 12 months outdoors. It can be seen that obvious migration has occurred, which has led to a decrease in light conversion efficiency.
[0136] In summary, the chromophores, encapsulating films, glass, and photovoltaic modules with downconversion capabilities are synthesized by synthesizing chromophores with unsaturated double bonds, triple bonds, and silanes. With the help of crosslinking agents, these chromophores can chemically bond with the unsaturated bonds in the encapsulating film polymer or encapsulating glass, thus establishing a stable, high-temperature resistant, and chemically resistant network structure. This avoids the migration of chromophores due to temperature and concentration, effectively improving the light conversion efficiency of photovoltaic modules.
[0137] Based on the above-described preferred embodiments of the present invention, and through the foregoing description, those skilled in the art can make various changes and modifications without departing from the inventive concept. The technical scope of this invention is not limited to the contents of the specification, but must be determined according to the scope of the claims.
Claims
1. A chromophore with downconversion capability, characterized in that, Its structural formula is as follows: I-1; and / or Ⅰ-2 Where n is any integer from 0 to 100; E 0 Including any one of alkynyl, alkenyl, silane, silane-phenyl, and silylenyl; E 2 Selected from optionally substituted silanes, silenes, alkylenes, alkenylenes, oxy-oxides, silanes, heteroarylenes, ketones, and esters; G x Independently selected from optionally substituted alkylene, silene, optionally substituted olefin silene, ethynyl silene, alkenyl, optionally substituted ethynyl, optionally substituted aryl, optionally substituted silaneyl; and the A 1 A 2 Each is independently selected from the substituted aryl group or the substituted heteroaryl group; Or the A mentioned above 1 A 2 Each is independently selected from substituted silane heterocyclic groups, silane benzo[a]heterocyclic compound groups, or optionally substituted silane groups.
2. The chromophore with downconversion capability as described in claim 1, characterized in that, The heteroaryl group is selected from benzothiazolyl, benzoxazinyl, quinazolinyl, quinolinyl, isoquinolinyl, quinoxalinyl, pyridyl, pyrroleyl, purazolyl, indolyl, azinyl, pyrimidinyl, pyrazinyl, 2-pyridin-5-yl, furanyl, dibenzofuran-4-yl, benzofuranyl, dihydrophenodioxaneyl, benzothiophenyl, and dibenzothiophenyl.
3. The chromophore with downconversion capability as described in claim 1, characterized in that, The substitution in the substituted aryl group or the substituted heteroaryl group refers to one or more individual and independent functional groups selected from organosilicon derivatives including C1-C6 silyl, C1-C6 silenyl, C1-C6 silynyl, C3-C7 silanecycloalkyl, C2-C7 silanecycloalkenyl, silanized benzoheterocyclic, halosilane, silanol, silyl ether, siloxene, silyl ester, silaldehyde, benzylsilane, arylsilane, acylsilane, halosiloxane, silicone, silanecarbamate, aminosilane, cyanosilicon, mercaptosilane, nitrosilane, glycylsilane, thiosilane, hydrazinosilane, and ureosilane.
4. The chromophore with downconversion capability as described in claim 1, characterized in that, The silicon heterocyclic compound groups include, but are not limited to, silicon heterocyclic four-membered ring compound groups, silicon heterocyclic five-membered ring compound groups, and silicon heterophenyl groups; The silicon-substituted benzoheterocyclic compound groups include, but are not limited to, silicon-substituted four-membered ring benzoheterocyclic compound groups, silicon-substituted five-membered ring benzoheterocyclic compound groups, and silicon-substituted benzoheterocyclic compound groups; The silane-heterocyclic four-membered ring compound groups include, but are not limited to, silane-heterocyclic butene groups and silane-heterocyclic butyl groups; The silane-5-membered ring compound groups include, but are not limited to, silane-5-membered ring groups and silane-5-membered ring groups.
5. The chromophore with downconversion capability as described in claim 1, characterized in that, The substitution in the substituted silane heterocyclic group and the silane-substituted benzene heterocyclic compound group refers to one or more individual and independent functional groups selected from organosilicon derivatives including C1-C6 silane, C1-C6 silenyl, C1-C6 silynyl, C3-C7 silane heterocyclic alkyl, C2-C7 silane heterocyclic alkenyl, silane-substituted benzene heterocyclic, halosilane, silanol, silyl ether, siloxene, silyl ester, silaldehyde, benzylsilane, arylsilane, acylsilane, halosiloxane, silicone, silanecarbamate, aminosilane, cyanosilicon, mercaptosilane, nitrosilane, glycylsilane, thiosilane, hydrazinosilane, and ureosilane.
6. The chromophore with downconversion capability as described in claim 1, characterized in that, Its structural formula is as follows: II-1; and / or Ⅱ-2； Where n is any integer from 0 to 100; E 0 It is selected from alkynyl, alkenyl, silane, silane-phenyl, and silylene; E 1 Selected from optionally substituted silanes, silenes, alkylenes, alkenylenes, oxy-oxides, silanes, heteroarylenes, ketones, and esters; G x Independently selected from optionally substituted alkylene, optionally substituted alkylene silylene, alkylene silylene, alkenyl, optionally substituted alkylene silylene, optionally substituted arylene, optionally substituted silylene; R 1 Independently selected from any substituted siloxane, aminosilane, heterosilylphenyl, C1-C6 alkoxy, aryloxy, and amino; The optional substitution and the substitution referred to therein refer to one or more individual and independent functional groups selected from organosilicon derivatives including C1-C6 silyl groups, C1-C6 silene groups, C1-C6 silynyl groups, C3-C7 silane-heterocyclic alkyl groups, C2-C7 silane-heterocyclic alkenyl groups, halosilanes, silanol groups, siloxanes, siloxanes, silaldehydes, benzylsilanes, arylsilanes, acylsilanes, halosiloxanes, silicones, silane-carbene, aminosilanes, cyanosilicones, mercaptosilanes, nitrosilanes, glycylsilanes, thiosilanes, hydrazinosilanes, and ureosilanes.
7. An encapsulating film with downconversion capability, characterized in that, include: In the case of at least one luminescent dye and organic polymer material prepared from a chromophore with downconversion capability as described in any one of claims 1-6, the chromophore and the polymer material are cross-linked into a network structure during the lamination process, and the chromophore cannot migrate.
8. The encapsulating film with downconversion capability as described in claim 7, characterized in that, The thickness of the encapsulating film is 10-1000 μm; Furthermore, the mass percentage of the chromophore with downconversion capability is 0.01-2 wt%.
9. A type of glass with down-conversion capability, characterized in that, include: At least one surface contains a luminescent dye prepared from a chromophore with downconversion capability as described in any one of claims 1-6.
10. A photovoltaic module, characterized in that, include: The encapsulating film with downconversion capability as described in claim 7 and / or the glass with downconversion capability as described in claim 9.