TWI605682B - Quantum? dots-containing? flexible? luminescent solar concentrators? and the preparation method thereof - Google Patents

Description

Flexible quantum dot solar concentrating sheet and preparation method thereof

The invention relates to a quantum dot solar concentrating sheet for a solar concentrator and a preparation method thereof, in particular to a flexible quantum dot solar concentrating sheet with high light transmittance and a preparation method thereof.

The most inexhaustible source of energy in nature, the most well-known in the world is solar energy. With the rise of environmental awareness, countries around the world are not vigorously developing various renewable energy sources. In particular, countries around the world have been rushing to use non-polluting solar energy to solve problems such as possible exhaustion of oil, natural gas, coal, and environmental hazards.

Today, the focus of solar energy utilization is focused on how to collect solar energy more efficiently, how to more efficiently converge solar energy, collect heat, generate electricity or combine them.

Solar concentrating is mainly used in solar photovoltaic systems; solar thermal collection is based on solar thermal energy, and is widely used in solar thermal power generation, solar heating and other systems.

Most of the concentrators used in conventional concentrating solar cells use lenses to concentrate light in a small area to improve power generation efficiency; however, because such systems must be equipped with a solar tracking system as a whole, such solar systems often have a volume. Large, heavy weight, not easy to mass produce, and difficult to apply to a variety of problems in home power generation systems.

In order to solve the above problems, in recent years, a quantum dot solar concentrating sheet composed of a quantum dot and an organic polymer material has been developed. Since such a quantum dot solar concentrating sheet is a transparent or translucent planar structure, and has excellent optical properties and function of concentrating power generation, it has become a leader of a new generation of solar concentrators, widely The modern building industry is heavily used.

However, quantum dot solar concentrating sheets still have many unsatisfactory defects, for example, the hard materials are easy to embrittle and break, the outdoor service life is not long, the weather is not resistant to weather, and it is difficult to process. These shortcomings require the joint efforts of members of the modern industry to overcome and solve them together.

Therefore, there is an urgent need to develop an excellent optical property that not only retains the original optical characteristics of the quantum dot solar concentrating sheet, but also is not easy to embrittle and break, has a long outdoor life, and is resistant to harsh weather, and also has an easy bending and folding. Novel flexible quantum dot solar concentrating sheet with curved nature, low manufacturing cost, easy processing and high economic efficiency.

In view of the above, the present inventors have diligently studied and searched for various possible solutions for solving the above-mentioned problems of the conventional technology, thereby developing a problem in which not only the conventional technology can be improved, but also the quantum dots can be retained. In addition to the original optical characteristics of the concentrating sheet, it is not easy to embrittle and break, has long outdoor life, and is resistant to harsh weather. It also has excellent flexing properties for easy bending and folding, low manufacturing cost, easy processing and high processing. The novel and flexible quantum dot solar concentrating sheet of economic efficiency has heretofore completed the present invention.

In other words, according to an embodiment of the present invention, a quantum dot solar concentrating sheet is provided, which is a flexible solar concentrating sheet (FLSC) composed of at least one optical layer and a plurality of quantum dot particles, wherein The optical layer is composed of a light guiding material and a hardener, and at least one of the light guiding material and the hardener is polydimethyl siloxane (PDMS), polyvinyl butyral (PVB), or Polyvinyl alcohol (PVA), or a mixture thereof; the quantum dot particles are composed of indium sulphide/zinc sulfide (CIS/ZnS); and at room temperature, the solar concentrator has a full curl Cylindrical flexibility; and after making a sheet-like FLSC of 30 mm (L) x 30 mm (W) x 5 mm (T), bend it in half until the FLSC cracks or breaks, measure this time The minimum angle θ formed by the bending of the fold is the same as the minimum angle θ (flexible angle) measured by the flaky FLSC without cracking or breaking. 60 degrees.

Moreover, according to another aspect of the present invention, the size and shape of the flexible quantum dot solar concentrating sheet provided by the present invention are not particularly limited. For example, it may be 30 mm (L) x 30 mm (for example). The sheet shape of W) may be a rectangular shape of 10 mm (L) x 30 mm (W), and of course, may be a cylindrical column or the like.

Secondly, according to another aspect of the present invention, in the flexible quantum dot solar concentrating sheet provided by the present invention, the position of the quantum dot is not particularly limited. For example, the quantum dots may be present on the surface layer, the lower surface layer, or the intermediate layer above the concentrating sheet.

Moreover, according to another aspect of the present invention, the minimum angle θ (flexible angle) of the flexible quantum dot solar concentrating sheet provided by the present invention is not particularly limited, for example, generally not greater than 60 degrees; preferably not more than 45 degrees; more preferably not more than 30 degrees; particularly preferably not more than 15 degrees; optimally not more than 5 degrees.

Furthermore, according to another embodiment of the present invention, a flexible quantum dot solar concentrating sheet can be provided, wherein when the optical layer is two layers, a plurality of quantum dot particles are dispersed in at least one or two layers thereof. .

In addition, according to other embodiments of the present invention, a flexible quantum dot solar concentrating sheet can be provided, wherein when the optical layer is three layers, a plurality of quantum dot particles are dispersed in at least one or more layers.

In addition, according to another aspect of the present invention, a flexible quantum dot solar concentrating sheet having three layers of optical layers may be provided, wherein a plurality of quantum dot particles are dispersed in one of the most intermediate layers.

Moreover, according to another aspect of the present invention, a flexible quantum dot solar concentrating sheet having three layers of optical layers may be further provided, wherein the plurality of quantum dot particles are the outermost layer dispersed on at least one side.

In addition, according to another aspect of the present invention, a flexible quantum dot solar concentrating sheet having three layers of optical layers may be provided, wherein the plurality of quantum dot particles are the outermost layers dispersed on both sides.

Furthermore, another specific embodiment of the flexible quantum dot solar concentrating sheet according to the present invention can be suitably used as a light guiding material and/or a hardening agent used as a constituent component of the optical layer of the present invention, as long as it is capable of The material which has both light transmissivity and light guiding property is not particularly limited. For example, a flexible light transmissive material that is generally known in the prior art to which the present invention pertains can be used.

The above flexible light transmissive material is, for example, but not limited to, polydimethyl methoxy oxane (PDMS), polyvinyl butyral (PVB), polyvinyl alcohol (PVA); polyterephthalic acid; Polyester resin such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN); polymethyl methacrylate (PMMA), etc. Polyacrylate resin; polyimide resin; polyethylene (PE) or polypropylene (PP), polycycloolefin resin (polycycloolefmresin), polycarbonate resin (polycarbonate) A resin, a polyolefin resin such as a polyurethane resin, a triacetate cellulose (TAC), or a mixture thereof.

In the above examples of the flexible light-transmitting material, it is preferred to use polydimethyl siloxane (PDMS), polyvinyl butyral (PVB), polyvinyl alcohol (PVA), polyethylene terephthalate. Diester, polymethyl methacrylate, polycycloolefin resin, or cellulose triacetate, or a mixture thereof, more preferably polydimethyl methoxy oxane (PDMS), polyvinyl butyral (PVB) , polyvinyl alcohol (PVA), or polyethylene terephthalate, or a mixture thereof; preferably polydimethyl siloxane (PDMS), polyethylene Enol butyral (PVB), or polyvinyl alcohol (PVA), or a mixture thereof, is used as a source of a light guiding material and/or a hardening agent which is a constituent of the optical layer of the present invention.

Moreover, according to another embodiment of the flexural quantum dot solar concentrating sheet of the present invention, the source of the light guiding material and the hardener may be the same or different, preferably the light guiding material and the hardener. At least one of them is polydimethyl methoxy oxane (PDMS), polyvinyl butyral (PVB), or polyvinyl alcohol (PVA); more preferably, both the light guiding material and the hardening agent are poly Dimethyl decane (PDMS), polyvinyl butyral (PVB), or polyvinyl alcohol (PVA).

A method for preparing a flexible quantum dot solar concentrating sheet, comprising: uniformly mixing and mixing a light guiding material (X), a hardener (Y), and a quantum dot luminescent material (Z), pouring the module into a module and The vacuum is eliminated without bubbles, and then baked in an oven preheated to the first heating temperature for baking after the first hardening forming time, and then the temperature is further increased to the second heating temperature for baking, and after the second hardening forming time, the cooling is left. Obtaining a solar concentrating sheet (FLSC); wherein the ratio of the light guiding material (X) and the hardener (Y) is, by weight, the ratio of X:Y is in the range of 20:3 to 3:20; the light guiding material (X), the addition ratio of the quantum dot luminescent material (Z), the ratio of X:Z is in the range of 10:1 to 1:10 by weight; the hardener (Y), the quantum dot luminescent material (Z) The addition ratio, the ratio of Y:Z is in the range of 3:2 to 2:3 by weight; and at room temperature, the solar concentrating sheet (FLSC) has flexibility capable of being completely curled into a cylindrical shape. .

Moreover, according to other embodiments of the present invention, a flexible quantum dot solar concentrating sheet may be further provided, wherein at least one of the light guiding material (X) and the hardener (Y) is polydimethyl Hydroxane material (PDMS), polyethylene Alcohol butyral (PVB), or polyvinyl alcohol (PVA), or a mixture thereof; quantum dot luminescent materials include materials based on indium sulphide/zinc sulfide quantum dots (CIS/ZnS)

Furthermore, according to another embodiment of the present invention, a quantum dot solar concentrating sheet may be additionally provided, wherein the first heating temperature is in the range of 50 to 90 ° C, and/or the first hardening forming time is 6 hours to a range of 36 hours; preferably, the first heating temperature is in the range of 55 to 85 ° C, and/or the first hardening forming time is in the range of 7 hours to 33 hours; more preferably, the first heating temperature is In the range of 60 to 80 ° C, and/or the first hardening forming time is in the range of 8 hours to 30 hours; particularly preferably, the first heating temperature is in the range of 60 to 75 ° C, and/or the first hardening is formed. The time is in the range of 8 hours to 28 hours.

In addition, according to still another specific embodiment of the present invention, a flexible quantum dot solar concentrating sheet may be further provided, wherein the second heating temperature is in the range of 80 to 160 ° C, and/or the second hardening forming time It is in the range of 0.5 hours to 24 hours; preferably, the second heating temperature is in the range of 85 to 155 ° C, and/or the second hardening forming time is in the range of 0.7 to 22 hours; more preferably: The heating temperature is in the range of 90 to 150 ° C, and/or the second hardening forming time is in the range of 0.9 to 20 hours; particularly preferably, the second heating temperature is in the range of 95 to 145 ° C, and/or The second hardening forming time is in the range of 1.0 hour to 18 hours.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a typical manufacturing process of an embodiment of a flexible quantum dot solar concentrating sheet according to the present invention.

Fig. 2 is a photograph showing the results of a foldable test of a flexible quantum dot solar concentrating sheet according to an embodiment of the present invention.

Fig. 3 is a characteristic spectrum diagram showing copper indium sulfide/zinc sulfide quantum dots obtained in Examples 1, 3 and 5 of the present invention.

Figure 4 is a graph showing the characteristic spectra of copper indium sulfide/zinc sulfide quantum dots prepared in Examples 2 and 4 of the present invention.

Figure 5 is a photograph showing a flexible quantum dot solar concentrating sheet prepared in accordance with Examples 1-5 of the present invention; wherein the symbols 1, 2, 3, 4, and 5 are respectively representative of Examples 1, 2, and 3; , 4, 5 made of flexible quantum dot solar concentrating sheet.

The structure, preparation method and the like of the flexible quantum dot solar concentrating sheet of the present invention will be specifically described below with reference to the accompanying drawings.

Hereinafter, the respective components of the optical layer and the like in the flexible quantum dot solar concentrating sheet of the present invention, and the use thereof, the light guiding material, the curing agent, the quantum dot particles and the like will be described; however, The invention is of course not limited to those described herein.

In addition, it will be apparent to those skilled in the art that the present invention can be made without departing from the spirit and scope of the invention. Also included in the scope of the patent application of the present invention.

Further, the use of the flexible quantum dot solar concentrating sheet of the present invention is not particularly limited, and for example, it can be used as a power source for a solar panel, a light guide plate, a power source for an electronic component, and a constituent element of a battery. Wait.

Hand Flexibility Test

The 30 mm (L) x 30 mm (W) x 5 mm (T) flexible quantum dot solar concentrating sheet (FLSC) obtained in the examples was crimped by finger force at room temperature, by means of energy Whether it is rolled into a cylindrical shape to judge its flexibility, it is judged to be good flexibility when it is very easy to curl (○); it is judged to be moderately flexible when it is difficult to curl or curl (△); When it is not possible to curl, it is judged that it has no flexibility (x).

"Foldable test"

The 30 mm (L) x 30 mm (W) x 5 mm (T) flexible quantum dot solar concentrator (FLSC) obtained in the examples was folded in half at room temperature and bent. Before folding until the FLSC is cracked or broken, as shown in Fig. 2, the minimum angle θ formed by bending in half is measured, and it is used as the foldable angle of the sheet-like FLSC without cracking or breaking.

Next, based on the results of the above-mentioned measurement of the foldable angle (minimum angle θ), the flexibility is judged according to the following criteria.

(1) When the minimum angle θ is less than 30 degrees, it is judged to be good and easy to fold (◎); (2) When the minimum angle θ is between 31 degrees and 60 degrees, it is judged to be moderately easy to fold (○); (3) When the minimum angle θ is between 61 degrees and 90 degrees, it is judged to be generally easy to fold (Δ); (4) When the minimum angle θ is between 91 degrees and 120 degrees, it is judged that it is not easy to fold or the difference in flexibility (Δ△△); (5) when the minimum angle θ is from 121 degrees to 165 degrees, it is judged that it is difficult to fold in half. Or inferior flexibility (×); (6) When the minimum angle θ is greater than 166 degrees, it is judged that it is not foldable or has no flexibility (×××).

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a typical manufacturing process of an embodiment of a flexible quantum dot solar concentrating sheet according to the present invention.

Hereinafter, a reference example for producing the flexible quantum dot solar concentrating sheet of the present invention will be described with reference to Fig. 1 .

Example 1

Preparation of Copper Indium Sulfide/Zinc Sulfide Quantum Dots (CuInS ₂ /ZnS QDs) Solution

First, 1.7 mmol of Copper (I) iodide (CuI, 98%) and 17 ml of n-dodecylthiol (DDT, 98.0%) were uniformly stirred and mixed, and then transferred to a microwave oven (manufactured by Anton Paar Co., Monowave 300) at a temperature. Heating at 120 ° C for 10 minutes gave a 0.1 mM Cu-DDT solution.

Next, 3.4 mmol of sulfur (S, 99.5%) and 17 ml of n-octadecene (ODE, 90%) were uniformly stirred and mixed, and then transferred to a microwave oven (manufactured by Anton Paar Co., Monowave 300), and heated at a temperature of 160 ° C. A 0.2 mM S-ODE solution was allowed for 10 minutes.

Next, 6.8 mmol of zinc acetate (Zn(Ac) ₂ , 99.5%), 5 ml of oleylamine (OAm, 70%), and 12 ml of n-octadecene (ODE, 90%) was uniformly stirred and mixed, and then transferred into a microwave oven (manufactured by Anton Paar Co., Monowave 300), and heated at a temperature of 160 ° C for 10 minutes to obtain a 0.4 mM Zn-OAm-ODE solution.

Then, 0.2 mmol of indium (III) acetate (In (Ac) 3, 99.99%), 1 ml of the above-prepared 0.1 mM Cu-DDT, and 0.6 ml of oleic acid (OA) were prepared. , 90%), 1 ml of the above prepared 0.2 mM S-ODE, 3 ml of n-octadecene (ODE, 90%), and 1 ml of n-dodecanethiol (n- Dodecylthiol) (DDT, 98.0%) was uniformly stirred and mixed, transferred to a microwave oven (manufactured by Anton Paar Co., Monowave 300), and heated at a temperature of 230 ° C for 5 minutes to obtain a copper indium sulfide (CIS) quantum dot solution.

Next, 3 ml of the above-prepared 0.4 mM Zn-OAm-ODE solution and the above prepared copper indium sulfide (CIS) quantum dot solution were placed in a test tube, and the tube was transferred to a microwave oven (manufactured by Anton Paar Co., Ltd., In Monowave 300), heating was continued at a temperature of 230 ° C for 10 minutes to obtain a crude copper indium sulfide/zinc sulfide quantum dot (CuInS ₂ /ZnS QDs) solution.

Continuing, in a 50 ml centrifuge tube, 9.6 ml of the above prepared copper indium sulfur/zinc sulfide quantum dot (CuInS ₂ /ZnS QDs) solution, 30 ml of acetone, and then continuously centrifuged for 15 min in a centrifuge of 4000 rpm. A solid having copper indium sulfide/zinc sulfide quantum dots (CuInS ₂ /ZnS QDs) was obtained.

Moreover, the quantum benefit of the copper indium sulfide/zinc sulfide quantum dots (CuInS ₂ /ZnS QDs) prepared by Shangcheng is 40%, and has optical characteristics such as broadband blue-violet absorption and broadband red-orange light emission, as shown in FIG. The characteristic spectrum is that the black line is the absorption spectrum, the red is the emission spectrum, and the emission spectrum peak position is 625 nm, so that the blue-violet light can be converted into red light.

Preparation of Solar Concentrating Films

0.79 g of the above prepared copper indium sulfide/zinc sulfide quantum dot (CuInS ₂ /ZnS QDs) solid was dispersed in 20 ml of chloroform to prepare a mixed solution having a concentration of 39.5 mg/mL, and 10 ml of polyoxyxene elasticity. Agent A (trade name: Sylgard 184 A, the main component is PDMS (polydimethyl methoxy oxane), silicone elastomers A), and 1.5 ml of polyoxyxide elastomer B (trade name: Sylgard 184B, the main component is PDMS (polydimethyl siloxane), silicone elastomers B) After mixing and mixing, pour into a mold of 30mm (L) x 30mm (W) x 5mm (T), transfer to a vacuum drying chamber, and use vacuum pump (LABOPORT) ® N810.3 FT.18) Pumping for 30 minutes creates a vacuum to remove surface bubbles.

Next, the module with the surface bubbles removed was placed in a heat flow oven, baked at 70 ° C for 12 hours to remove chloroform, and then heated to 120 ° C for 2 hours for hardening. After the formation, the flexible quantum dot solar concentrating sheet (FLSC1) of the first embodiment was obtained by cooling off the mold, as shown in FIG.

Next, an optical test was performed on the above-obtained flexible quantum dot solar concentrator (FLSC1), and the absorbance was measured to be 0.7. Thus, according to Beer-Lambert Law's law "A = ε × C × d, (where A is Absorbance, ε is Mohr absorption coefficient (M ^-1 cm ^-1 , 2 x 10 ⁵ ), C For the concentration (M), d is the optical path length (cm) and the thickness is 0.5 cm. The calculation shows that the copper indium sulfide/zinc sulfide quantum dots in the solar concentrator (FLSC1) obtained in the first embodiment ( The concentration of CuInS ₂ /ZnS QDs) was 7 μM.

Next, the obtained flexible quantum dot solar concentrating sheet was subjected to a hand-flexibility test and a foldability test. As a result, the sheet-like solar concentrating sheet (FLSC1) of 30 mm (L) x 30 mm (W) x 5 mm (T) of the present Example 1 has a shape capable of being completely curled into a cylindrical shape at room temperature; The minimum angle θ (the foldable angle) of the crack or the fracture was 28 degrees, and thus the solar concentrating sheet (FLSC1) of the first embodiment was judged to have excellent hand flexibility and very good foldability. The physical properties of the solar concentrator (FLSC1) obtained as described above are shown in Table 1.

Example 2

Preparation of Copper Indium Sulfide/Zinc Sulfide Quantum Dots (CuInS ₂ /ZnS QDs) Solution

First, 1.7 mmol of Copper (I) iodide (CuI, 98%) and 17 ml of n-dodecylthiol (DDT, 98.0%) were uniformly stirred and mixed, and then transferred to a microwave oven (manufactured by Anton Paar Co., Monowave 300) at a temperature. Heating at 120 ° C for 10 minutes gave a 0.1 mM Cu-DDT solution.

Next, 3.4 mmol of sulfur (S, 99.5%) and 17 ml of n-octadecene (ODE, 90%) were uniformly mixed and mixed, and then transferred to a microwave oven (manufactured by Anton Paar Co., Monowave 300) at a temperature of 160 ° C. Heat for 10 minutes to bring to a 0.2 mM S-ODE solution.

Next, 6.8 mmol of zinc acetate (Zn(Ac) ₂ , 99.5%), 5 ml of oleylamine (OAm, 70%), and 12 ml of n-octadecene (ODE, 90%) was uniformly stirred and mixed, and then transferred into a microwave oven (manufactured by Anton Paar Co., Monowave 300), and heated at a temperature of 160 ° C for 10 minutes to obtain a 0.4 mM Zn-OAm-ODE solution.

Then, 0.2 mmol of indium (III) acetate (In (Ac) 3, 99.99%), 1 ml of the above-prepared 0.1 mM Cu-DDT, and 0.6 ml of oleic acid (OA) were prepared. , 90%), 1 ml of the above prepared 0.2 mM S-ODE, 3 ml of n-octadecene (ODE, 90%), and 1 ml of n-dodecanethiol (n- Dodecylthiol) (DDT, 98.0%) was uniformly stirred and mixed, transferred to a microwave oven (manufactured by Anton Paar Co., Monowave 300), and heated at a temperature of 230 ° C for 5 minutes to obtain a copper indium sulfide (CIS) quantum dot solution.

Next, 3 ml of the above-prepared 0.4 mM Zn-OAm-ODE solution and the above prepared copper indium sulfide (CIS) quantum dot solution were placed in a test tube, and the tube was transferred to a microwave oven (manufactured by Anton Paar Co., Ltd., In Monowave 300), heating was continued at a temperature of 230 ° C for 10 minutes to obtain a crude copper indium sulfide/zinc sulfide quantum dot (CuInS ₂ /ZnS QDs) solution.

Continuing, in a 50 ml centrifuge tube, 9.6 ml of the above prepared copper indium sulfur/zinc sulfide quantum dot (CuInS ₂ /ZnS QDs) solution, 30 ml of acetone, and then continuously centrifuged for 15 min in a centrifuge of 4000 rpm. A solid precipitate having copper indium sulfide/zinc sulfide quantum dots (CuInS ₂ /ZnS QDs) was obtained.

Moreover, the quantum benefit of the copper indium sulfide/zinc sulfide quantum dots (CuInS ₂ /ZnS QDs) prepared by Shangcheng is 40%, and has optical properties such as broadband blue-violet absorption and broadband red-orange emission, as shown in the figure. The characteristic spectrum, the black line is the absorption spectrum, the red is the emission spectrum, and the emission spectrum peak position is 690 nm, so that the blue-violet light can be converted into red light.

Preparation of Solar Concentrating Films

1.34 g of the above prepared copper indium sulfide/zinc sulfide quantum dot (CuInS ₂ /ZnS QDs) solid was dispersed in 20 ml of chloroform to prepare a mixed solution having a concentration of 67 mg/mL, and 10 ml of a polyoxyxanthene elastomer. A (trade name: Sylgard 184A, the main component is PDMS (polydimethyl methoxy oxane), silicone elastomers A), and 1.5 ml of polyoxyxide elastomer B (trade name: Sylgard 184 B, the main component is PDMS ( Polydimethyl siloxane, silicone elastomers B) After mixing and mixing, pour into a mold of 30mm (L) x 30mm (W) x 5mm (T), transfer to a vacuum drying chamber, and use vacuum pump (LABOPORT® N810.3 FT.18) A vacuum was applied for 30 min to remove surface bubbles.

Next, the module with the surface bubbles removed was placed in a heat flow oven, baked at 70 ° C for 12 hours to remove chloroform, and then heated to 120 ° C for 2 hours for hardening. After the formation, the flexible quantum dot solar concentrating sheet (FLSC2) of the second embodiment was obtained after cooling and demolding, as shown in FIG.

Next, an optical test was performed on the above-obtained flexible quantum dot solar concentrator (FLSC2), and the absorbance was measured to be 1.2. Thus, according to Beer-Lambert Law's law "A = ε × C × d, (where A is Absorbance, ε is Mohr absorption coefficient (M ^-1 cm ^-1 , 2 x 10 ⁵ ), C For the concentration (M), d is the optical path length (cm) and the thickness is 0.5 cm. The calculation shows that the copper indium sulfide/zinc sulfide quantum dots in the solar concentrator (FLSC2) prepared in the second embodiment ( The concentration of CuInS ₂ /ZnS QDs) was 12 μM.

Next, the obtained flexible quantum dot solar concentrating sheet was subjected to a hand-flexibility test and a foldability test. As a result, the sheet-like solar concentrating sheet (FLSC2) of 30 mm (L) x 30 mm (W) x 5 mm (T) of the present Example 2 has a shape capable of being completely curled into a cylindrical shape at room temperature; The minimum angle θ (which can be folded in half) of the crack or the fracture is 30 degrees, and thus it is judged that the solar concentrating sheet (FLSC2) of the second embodiment has excellent hand flexibility and very good foldability. The physical properties of the solar concentrator (FLSC2) obtained as described above are shown in Table 1.

Example 3

Preparation of Copper Indium Sulfide/Zinc Sulfide Quantum Dots (CuInS ₂ /ZnS QDs) Solution

First, 1.7 mmol of Copper (I) iodide (CuI, 98%) and 17 ml of n-dodecylthiol (DDT, 98.0%) were uniformly stirred and mixed, and then transferred to a microwave oven (manufactured by Anton Paar Co., Monowave 300) at a temperature of 120. The temperature was continued for 10 minutes at ° C to obtain a 0.1 mM Cu-DDT solution.

Next, 3.4 mmol of sulfur (S, 99.5%) and 17 ml of n-octadecene (ODE, 90%) were uniformly mixed and mixed, and then transferred to a microwave oven (manufactured by Anton Paar Co., Monowave 300) at a temperature of 160 ° C. Heat for 10 minutes to bring to a 0.2 mM S-ODE solution.

Next, 6.8 mmol of zinc acetate (Zn(Ac) ₂ , 99.5%), 5 ml of oleylamine (OAm, 70%), and 12 ml of n-octadecene (ODE, 90%) was uniformly stirred and mixed, and then transferred into a microwave oven (manufactured by Anton Paar Co., Monowave 300), and heated at a temperature of 160 ° C for 10 minutes to obtain a 0.4 mM Zn-OAm-ODE solution.

Then, 0.2 mmol of indium (III) acetate (In (Ac) 3, 99.99%), 1 ml of the above-prepared 0.1 mM Cu-DDT, and 0.6 ml of oleic acid (OA) were prepared. , 90%), 1 ml of the above prepared 0.2 mM S-ODE, 3 ml of n-octadecene (ODE, 90%), and 1 ml of n-dodecanethiol (n- Dodecylthiol) (DDT, 98.0%) was uniformly stirred and mixed, transferred to a microwave oven (manufactured by Anton Paar Co., Monowave 300), and heated at a temperature of 230 ° C for 5 minutes to obtain a copper indium sulfide (CIS) quantum dot solution.

Next, 3 ml of the above-prepared 0.4 mM Zn-OAm-ODE solution and the above prepared copper indium sulfide (CIS) quantum dot solution were placed in a test tube, and the tube was transferred to a microwave oven (manufactured by Anton Paar Co., Ltd., In Monowave 300), heating was continued at a temperature of 230 ° C for 10 minutes to obtain a crude copper indium sulfide/zinc sulfide quantum dot (CuInS ₂ /ZnS QDs) solution.

Continuing, in a 50 ml centrifuge tube, 9.6 ml of the above prepared copper indium sulfur/zinc sulfide quantum dot (CuInS ₂ /ZnS QDs) solution, 30 ml of acetone, and then continuously centrifuged for 15 min in a centrifuge of 4000 rpm. A solid precipitate having copper indium sulfide/zinc sulfide quantum dots (CuInS ₂ /ZnS QDs) was obtained.

Moreover, the quantum benefit of the copper indium sulfide/zinc sulfide quantum dots (CuInS ₂ /ZnS QDs) prepared by Shangcheng is 40%, and has optical characteristics such as broadband blue-violet absorption and broadband red-orange light emission, as shown in FIG. The characteristic spectrum is that the black line is the absorption spectrum, the red is the emission spectrum, and the excitation wavelength is at 625 nm, so that the blue-violet light can be converted into red light.

Preparation of Solar Concentrating Films

0.79 g of the above prepared copper indium sulfide/zinc sulfide quantum dot (CuInS ₂ /ZnS QDs) solid was dispersed in 20 ml of chloroform to prepare a mixed solution having a concentration of 39.5 mg/mL, and 10 ml of polyoxyxene elasticity. Agent A (trade name: Sylgard 184 A, the main component is PDMS (polydimethyl methoxy oxane), silicone elastomers A), and 1.5 ml of polyoxyxide elastomer B (trade name: Sylgard 184B, the main component is PDMS (polydimethyl siloxane), silicone elastomers B) After mixing and mixing, pour into a mold of 30mm (L) x 30mm (W) x 5mm (T), transfer to a vacuum drying chamber, and use vacuum pump (LABOPORT) ® N810.3 FT.18) Pumping for 30 minutes creates a vacuum to remove surface bubbles.

Next, the module with the surface bubbles removed was placed in a heat flow oven, baked at 70 ° C for 12 hours to remove chloroform, and then heated to 120 ° C for 6 hours for hardening. After the formation, the flexible quantum dot solar concentrating sheet (FLSC3) of the third embodiment was obtained after cooling and demolding, as shown in FIG.

Next, an optical test was performed on the above-obtained flexible quantum dot solar concentrator (FLSC3), and the absorbance was measured to be 3.0. Thus, according to Beer-Lambert Law's law "A = ε × C × d, (where A is Absorbance, ε is Mohr absorption coefficient (M ^-1 cm ^-1 , 2 x 10 ⁵ ), C For the concentration (M), d is the optical path length (cm) and the thickness is 0.5 cm. The calculation shows that the copper indium sulfide/zinc sulfide quantum dots in the solar concentrator (FLSC3) prepared in the third embodiment ( The concentration of CuInS ₂ /ZnS QDs) was 30 μM.

Next, the obtained flexible quantum dot solar concentrating sheet was subjected to a hand-flexibility test and a foldability test. As a result, the sheet-like solar concentrating sheet (FLSC3) of 30 mm (L) x 30 mm (W) x 5 mm (T) of the present Example 3 has a shape capable of being completely curled into a cylindrical shape at room temperature; The minimum angle θ (the foldable angle) of the crack or the fracture is 38 degrees, and thus it is judged that the solar concentrating sheet (FLSC3) of the third embodiment has excellent hand flexibility and medium versatility. The physical properties of the solar concentrator (FLSC3) obtained as described above are shown in Table 1.

Example 4

Preparation of Copper Indium Sulfide/Zinc Sulfide Quantum Dots (CuInS ₂ /ZnS QDs) Solution

First, 1.7 mmol of Copper (I) iodide (CuI, 98%) and 17 ml of n-dodecylthiol (DDT, 98.0%) were uniformly stirred and mixed, and then transferred to a microwave oven (manufactured by Anton Paar Co., Monowave 300) at a temperature. Heating at 120 ° C for 10 minutes gave a 0.1 mM Cu-DDT solution.

Next, 3.4 mmol of sulfur (S, 99.5%) and 17 ml of n-octadecene (ODE, 90%) were uniformly mixed and mixed, and then transferred to a microwave oven (manufactured by Anton Paar Co., Monowave 300) at a temperature of 160 ° C. Heat for 10 minutes to bring to a 0.2 mM S-ODE solution.

Next, 6.8 mmol of zinc acetate (Zn(Ac) ₂ , 99.5%), 5 ml of oleylamine (OAm, 70%), and 12 ml of n-octadecene (ODE, 90%) was uniformly stirred and mixed, and then transferred into a microwave oven (manufactured by Anton Paar Co., Monowave 300), and heated at a temperature of 160 ° C for 10 minutes to obtain a 0.4 mM Zn-OAm-ODE solution.

Then, 0.2 mmol of indium (III) acetate (In (Ac) 3, 99.99%), 1 ml of the above-prepared 0.1 mM Cu-DDT, and 0.6 ml of oleic acid (OA) were prepared. , 90%), 1 ml of the above prepared 0.2 mM S-ODE, 3 ml of n-octadecene (ODE, 90%), and 1 ml of n-dodecanethiol (n- Dodecylthiol) (DDT, 98.0%) was uniformly stirred and mixed, transferred to a microwave oven (manufactured by Anton Paar Co., Monowave 300), and heated at a temperature of 230 ° C for 5 minutes to obtain a copper indium sulfide (CIS) quantum dot solution.

Next, 3 ml of the above-prepared 0.4 mM Zn-OAm-ODE solution and the above prepared copper indium sulfide (CIS) quantum dot solution were placed in a test tube, and the tube was transferred to a microwave oven (manufactured by Anton Paar Co., Ltd., In Monowave 300), heating was continued at a temperature of 230 ° C for 10 minutes to obtain a crude copper indium sulfide/zinc sulfide quantum dot (CuInS ₂ /ZnS QDs) solution.

Continuing, in a 50 ml centrifuge tube, 9.6 ml of the above prepared copper indium sulfur/zinc sulfide quantum dot (CuInS ₂ /ZnS QDs) solution, 30 ml of acetone, and then continuously centrifuged for 15 min in a centrifuge of 4000 rpm. A solid precipitate having copper indium sulfide/zinc sulfide quantum dots (CuInS ₂ /ZnS QDs) was obtained.

Moreover, the quantum benefit of the copper indium sulfide/zinc sulfide quantum dots (CuInS ₂ /ZnS QDs) prepared by Shangcheng is 40%, and has optical properties such as broadband blue-violet absorption and broadband red-orange emission, as shown in FIG. The characteristic spectrum is that the black line is the absorption spectrum, the red is the emission spectrum, and the excitation wavelength is at 690 nm, so that the blue-violet light can be converted into red light.

Preparation of Solar Concentrating Films

1.34 g of the above prepared copper indium sulfide/zinc sulfide quantum dot (CuInS ₂ /ZnS QDs) solid was dispersed in 20 ml of chloroform to prepare a mixed solution having a concentration of 67 mg/mL, and 10 ml of a polyoxyxanthene elastomer. A (trade name: Sylgard 184 A, the main component is PDMS (polydimethyl methoxy oxane), silicone elastomers A), and 1.5 ml of polyoxyxide elastomer B (trade name: Sylgard 184 B, the main component is PDMS (polydimethyl siloxane), silicone elastomers B) After mixing and mixing, pour into a mold of 30mm (L) x 30mm (W) x 5mm (T), transfer to a vacuum drying chamber, and use vacuum pump (LABOPORT) ® N810.3 FT.18) Pumping for 30 minutes creates a vacuum to remove surface bubbles.

Next, the module with the surface bubbles removed was placed in a heat flow oven, baked at 70 ° C for 24 hours to remove chloroform, and then heated to 120 ° C for 12 hours for hardening. After the formation, the flexible quantum dot solar concentrating sheet (FLSC4) of the fourth embodiment was obtained after cooling and demolding, as shown in FIG.

Next, an optical test was performed on the above-obtained flexible quantum dot solar concentrator (FLSC4), and the absorbance was measured to be 4.2. Thus, according to Beer-Lambert Law's law "A = ε × C × d, (where A is Absorbance, ε is Mohr absorption coefficient (M ^-1 cm ^-1 , 2 x 10 ⁵ ), C For the concentration (M), d is the optical path length (cm) and the thickness is 0.5 cm. The calculation shows that the copper indium sulfide/zinc sulfide quantum dots in the solar concentrating sheet (FLSC4) prepared in the fourth embodiment ( The concentration of CuInS ₂ /ZnS QDs) was 42 μM.

Next, the obtained flexible quantum dot solar concentrating sheet was subjected to a hand-flexibility test and a foldability test. As a result, the sheet-like solar concentrating sheet (FLSC4) of 30 mm (L) x 30 mm (W) x 5 mm (T) of the present Example 4 has a shape capable of being completely curled into a cylindrical shape at room temperature; The minimum angle θ (the foldable angle) of the crack or the fracture was 47 degrees, and thus the solar concentrating sheet (FLSC4) of the fourth embodiment was judged to have excellent hand flexibility and moderately versatile. The physical properties of the solar concentrator (FLSC4) obtained as described above are shown in Table 1.

Example 5

Preparation of Copper Indium Sulfide/Zinc Sulfide Quantum Dots (CuInS ₂ /ZnS QDs) Solution

First, 1.7 mmol of Copper (I) iodide (CuI, 98%) and 17 ml of n-dodecylthiol (DDT, 98.0%) were uniformly stirred and mixed, and then transferred to a microwave oven (manufactured by Anton Paar Co., Monowave 300) at a temperature. Heating at 120 ° C for 10 minutes gave a 0.1 mM Cu-DDT solution.

Next, 3.4 mmol of sulfur (S, 99.5%) and 17 ml of n-octadecene (ODE, 90%) were uniformly mixed and mixed, and then transferred to a microwave oven (manufactured by Anton Paar Co., Monowave 300) at a temperature of 160 ° C. Heat for 10 minutes to bring to a 0.2 mM S-ODE solution.

Next, 6.8 mmol of zinc acetate (Zn(Ac) ₂ , 99.5%), 5 ml of oleylamine (OAm, 70%), and 12 ml of n-octadecene (ODE, 90%) was uniformly stirred and mixed, and then transferred into a microwave oven (manufactured by Anton Paar Co., Monowave 300), and heated at a temperature of 160 ° C for 10 minutes to obtain a 0.4 mM Zn-OAm-ODE solution.

Then, 0.2 mmol of indium (III) acetate (In (Ac) 3, 99.99%), 1 ml of the above-prepared 0.1 mM Cu-DDT, and 0.6 ml of oleic acid (OA) were prepared. , 90%), 1 ml of the above prepared 0.2 mM S-ODE, 3 ml of n-octadecene (ODE, 90%), and 1 ml of n-dodecanethiol (n- Dodecylthiol) (DDT, 98.0%) was uniformly stirred and mixed, transferred to a microwave oven (manufactured by Anton Paar Co., Monowave 300), and heated at a temperature of 230 ° C for 5 minutes to obtain a copper indium sulfide (CIS) quantum dot solution.

Next, 3 ml of the above-prepared 0.4 mM Zn-OAm-ODE solution and the above prepared copper indium sulfide (CIS) quantum dot solution were placed in a test tube, and the tube was transferred to a microwave oven (manufactured by Anton Paar Co., Ltd., In Monowave 300), heating was continued at a temperature of 230 ° C for 10 minutes to obtain a crude copper indium sulfide/zinc sulfide quantum dot (CuInS ₂ /ZnS QDs) solution.

Continuing, in a 50 ml centrifuge tube, 9.6 ml of the above prepared copper indium sulfur/zinc sulfide quantum dot (CuInS ₂ /ZnS QDs) solution, 30 ml of acetone, and then continuously centrifuged for 15 min in a centrifuge of 4000 rpm. A solid precipitate having copper indium sulfide/zinc sulfide quantum dots (CuInS ₂ /ZnS QDs) was obtained.

Moreover, the quantum benefits of the copper indium sulfide/zinc sulfide quantum dots (CuInS ₂ /ZnS QDs) prepared above are 40%, and have optical characteristics such as broadband blue-violet light absorption and broadband red-orange light emission, as shown in FIG. The characteristic spectrum is that the black line is the absorption spectrum, the red is the emission spectrum, and the excitation wavelength is at 625 nm, so that the blue-violet light can be converted into red light.

Preparation of Solar Concentrating Films

0.79 g of the above prepared copper indium sulfide/zinc sulfide quantum dot (CuInS ₂ /ZnS QDs) solution was dispersed in 20 ml of chloroform to prepare a mixed solution having a concentration of 39.5 mg/mL, and 10 ml of polyoxyxene elasticity. Agent A (trade name: Sylgard 184 A, main component is PDMS (polydimethyl methoxy oxane), silicone elastomers A), and 1.5 ml of polyoxyxide elastomer B (trade name: Sylgard 184 B, the main component is PDMS (polydimethyl phthalocyanine), silicone elastomers B) After mixing and mixing, pour into a mold of 30mm (L) x 30mm (W) x 5mm (T), transfer to a vacuum drying chamber, and use a vacuum pump ( LABOPORT® N810.3 FT.18) A vacuum was applied for 30 min to remove surface bubbles.

Next, the module with the surface bubbles removed was placed in a heat flow oven, baked at 70 ° C for 24 hours to remove chloroform, and then heated to 120 ° C for 12 hours for hardening. After the formation, the flexible quantum dot solar concentrating sheet (FLSC5) of the fifth embodiment was obtained after cooling and demolding, as shown in FIG.

Next, an optical test was performed on the above-obtained flexible quantum dot solar concentrator (FLSC5), and the absorbance was measured to be 4.0. Thus, according to Beer-Lambert Law's law "A = ε × C × d, (where A is Absorbance, ε is Mohr absorption coefficient (M ^-1 cm ^-1 , 2 x 10 ⁵ ), C For the concentration (M), d is the optical path length (cm) and the thickness is 0.5 cm. The calculation shows that the copper indium sulfide/zinc sulfide quantum dots in the solar concentrating sheet (FLSC5) prepared in the fifth embodiment ( The concentration of CuInS ₂ /ZnS QDs) was 40 μM.

Next, the obtained flexible quantum dot solar concentrating sheet was subjected to a hand-flexibility test and a foldability test. As a result, the sheet-like solar concentrating sheet (FLSC5) of 30 mm (L) x 30 mm (W) x 5 mm (T) of the present Example 5 has a shape capable of being completely curled into a cylindrical shape at room temperature; The minimum angle θ (the foldable angle) of the crack or the fracture was 45 degrees, and thus the solar concentrating sheet (FLSC5) of the fifth embodiment was judged to have excellent hand flexibility and moderately versatile. The physical properties of the solar concentrator (FLSC5) obtained as described above are shown in Table 1.

From the results of Table 1 above, it is apparent that the solar concentrating sheets (FLSC) obtained in Examples 1 to 5 are evaluated to the highest level of excellence (○) in the hand-flexibility test, showing Good curling property, easy to store without occupying space, very favorable for transportation, and can effectively reduce costs. Moreover, the minimum angle θ (degrees) of each of the examples measured in the foldability test is between 28 and 47 degrees, showing good good foldability, no cracking or difficulty in breaking. Therefore, it is extremely useful in industrial applications.

From the examples of Embodiment 1 to Embodiment 5, it can be confirmed that the novel flexible quantum dot solar concentrating sheet of the present invention can simultaneously have less brittle fracture, long outdoor service life, and resistance to harsh weather, and also has both The utility model has the advantages of easy bending, excellent flexing property of folding, low manufacturing cost, easy processing and high economical efficiency, and thus the novel flexible quantum dot solar concentrating sheet of the invention can be used, in addition to retaining quantum dot solar concentrating In addition to the original optical characteristics of the light sheet, the above problems of the conventional technology can be improved.

Although the content of the present invention has been described in detail by way of examples as described above, the present invention is not limited to the embodiments. Therefore, the scope of protection to be covered in this case also includes the scope of the patent application described below and the scope defined by it.

A person skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention; for example, combining or modifying the technical contents exemplified in the foregoing embodiments. As a new embodiment, these embodiments are of course considered as belonging to the present invention.

Claims (10)

A quantum dot solar concentrating sheet, which is a flexible solar concentrating sheet (FLSC) composed of at least one optical layer and a plurality of quantum dot particles, wherein the optical layer is composed of a light guiding material and a hardener. The composition, at least one of the light guiding material and the hardener is polydimethyl siloxane (PDMS), polyvinyl butyral (PVB), or polyvinyl alcohol (PVA), or a mixture thereof The quantum dot particle is composed of indium tin sulfide/zinc sulfide (CIS/ZnS); and at room temperature, the solar concentrating sheet has flexibility capable of being completely curled into a cylindrical shape; After 30 mm (L) x 30 mm (W) x 5 mm (T) of the flaky FLSC, bend it in half until the FLSC is cracked or broken, and measure the minimum angle θ formed by the bending fold. As the flaky FLSC, the smallest angle θ (flexible angle) measured is not more than 60 degrees in the case where the deflection angle of cracks or breakage does not occur. The flexible quantum dot solar concentrating sheet according to claim 1, wherein when the optical layer is two layers, the plurality of quantum dot particles are at least one or two layers dispersed therein. The flexible quantum dot solar concentrating sheet according to claim 1, wherein when the optical layer is three layers, the plurality of quantum dot particles are dispersed in at least one or more layers. The flexible quantum dot solar concentrating sheet according to claim 1, wherein when the optical layer is three layers, the plurality of quantum dot particles are dispersed in one of the most intermediate layers. The flexible quantum dot solar concentrating sheet according to claim 1, wherein when the optical layer is three layers, the plurality of quantum dot particles are the outermost layer dispersed on at least one side. The flexible quantum dot solar concentrating sheet according to claim 1, wherein when the optical layer is three layers, the plurality of quantum dot particles are the outermost layer dispersed on both sides. A method for preparing a flexible quantum dot solar concentrating sheet, comprising: uniformly mixing and mixing a light guiding material (X), a hardener (Y), and a quantum dot luminescent material (Z), pouring the module into a module and The vacuum is eliminated without bubbles, and then baked in an oven preheated to the first heating temperature for baking after the first hardening forming time, and then the temperature is further increased to the second heating temperature for baking, and after the second hardening forming time, the cooling is left. Obtaining a solar concentrating sheet (FLSC); wherein the ratio of the light guiding material (X) and the hardener (Y) is, by weight, the ratio of X:Y is in the range of 20:3 to 3:20; the light guiding material (X), the addition ratio of the quantum dot luminescent material (Z), the ratio of X:Z is in the range of 10:1 to 1:10 by weight; the hardener (Y), the quantum dot luminescent material (Z) The addition ratio, the ratio of Y:Z is in the range of 3:2 to 2:3 by weight; and at room temperature, the solar concentrating sheet (FLSC) has flexibility capable of being completely curled into a cylindrical shape. . The method for preparing a flexible quantum dot solar concentrating sheet according to claim 7, wherein at least one of the light guiding material (X) and the hardener (Y) is a polydimethyl siloxane material (PDMS) ), polyvinyl butyral (PVB), or polyethylene Enol (PVA), or a mixture thereof; quantum dot luminescent materials include materials based on indium sulphide/zinc sulfide quantum dots (CIS/ZnS). The method for producing a quantum dot solar concentrating sheet according to claim 7, wherein the first heating temperature is in the range of 50 to 90 ° C; and the first hardening forming time is in the range of 6 hours to 36 hours. The method for preparing a flexible quantum dot solar concentrating sheet according to claim 7, wherein the second heating temperature is in the range of 80 to 160 ° C; and the second hardening forming time is in the range of 0.5 to 24 hours.