KR20150137730A - Method for manufacturing natural dyes for dye-sensitized solar cell - Google Patents

Abstract

The present invention relates to a manufacturing method of a natural dye for a dye-sensitized solar cell and, specifically, to a manufacturing method of a natural dye for a dye-sensitized solar cell, which is easily stored for a long time, and can be easily used because the natural dye used in natural dye adsorption of a photoelectrode for the dye-sensitized solar cell is produced in a powder type through extraction, concentration, enzyme treatment, powdering processes.

Description

METHOD FOR MANUFACTURING NATURAL DYES FOR DYE-SENSITIZED SOLAR CELL [0002]

The present invention relates to a process for producing a natural dye for a dye-sensitized solar cell, and more particularly, to a process for producing a natural dye for use in dye-sensitized solar cells by extracting, concentrating, The present invention relates to a method for producing a natural dye for a dye-sensitized solar cell.

Recently, various researches have been carried out to replace existing fossil fuels in order to solve the energy problems faced. Extensive research is underway to utilize natural energy such as wind, nuclear, and solar power to replace petroleum resources that are depleted within several decades. Among these solar cells, unlike other energy sources, the resources are infinite and environmentally friendly. Since the development of Se solar cells in 1983, recently, silicon solar cells have been spotlighted.

However, such a silicon solar cell is difficult to be put to practical use because the production cost is extremely high, and it is also difficult to improve the cell efficiency. In order to overcome these problems, development of a dye-sensitized solar cell having a remarkably low production cost has been actively studied.

A representative example of the dye-sensitized photovoltaic cell which is most well-known in the art is represented by a photoelectric chemical solar cell published by Gratzel et al., Switzerland in 1991. In general, a photosensitive- A photoelectrode mainly composed of metal oxide nanoparticles having a wide band gap energy to which a dye is adsorbed, a counter electrode catalyzed by platinum (Pt), and an electrolyte filled therebetween Solution.

When sunlight enters the dye-sensitized solar cell in the direction of the photo-electrode, the photo-excited state of the dye is absorbed by the photosensitive dye having a specific absorption wavelength. Here, the excited electrons are injected into the conduction band of the metal oxide due to the difference in the energy state, and diffuse to the electrode due to the difference in concentration of the injected electrons. The electrons in the electrode flow to the external circuit to transfer the electric energy, and when the electric energy is transmitted, the energy is low and the electrode moves to the counter electrode. Then, the photosensitive dye, which is injected with electrons into the metal oxide, receives electrons from the electrolyte solution as much as the number of transferred electrons and returns to the original state. In this case, the electrolyte used is a catalytic reaction (oxidation- And transmits electrons to the photosensitive dye.

However, the ruthenium (Ru) system is mainly used as a dye which is a key material for generating electrons by receiving light from a dye-sensitized solar cell, but ruthenium is the most rare material among the platinum group elements and is very expensive. Ruthenium-based dyes account for more than 20%, which is one of the major factors in the price competitiveness of dye-sensitized solar cells.

In addition, ruthenium has a problem in that it does not have many colors that can be represented, and thus it can not cope with the demanding needs of users in a wide variety of colors.

Therefore, it is urgent to develop alternative dyes which can replace conventional ruthenium dyes, and which are inexpensive, environmentally friendly, and capable of implementing various colors.

In response to this demand, Korean Patent Registration No. 10-1078369 (natural dye for dye-sensitized solar cell, dye-sensitized solar cell containing the same, and method for producing the same) has been developed and applied.

The natural dye for the dye-sensitized solar cell, the dye-sensitized solar cell comprising the same, and the method for producing the same, are prepared by using a dye extracted from a plant as a natural dye for a dye-sensitized solar cell, A dye-sensitized solar cell having a structure in which a nano-oxide layer, a counter electrode layer and an electrolyte layer are formed between the nano-oxide layer and the nano-oxide layer and the dye is adsorbed on the nano-oxide layer, Implementation is possible.

However, such a conventional natural dye for a dye-sensitized solar cell, a dye-sensitized solar cell including the dye-sensitized solar cell, and a manufacturing method thereof use only natural dyes.

Korean Patent Registration No. 10-1078369

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and an object of the present invention is to provide a dye- And a method for producing a natural dye for a dye-sensitized solar cell.

According to an aspect of the present invention,

An extracting step of adding a natural salt to an extractor and extracting it under a predetermined condition; A concentrating step of putting the extract liquid extracted from the extractor into a concentrator and concentrating the concentrate under a predetermined condition; An enzyme treatment step in which an enzyme is added to a concentrate; And a powdering step of filtering the enriched concentrated liquid to produce a natural dye powder.

Here, the extraction step is carried out one to two times at an extraction temperature of 30 to 98 DEG C, an extraction pressure of 0.0007 to 0.122 kgf / cm2, an extraction time of 30 to 130 minutes, and depending on the characteristics of the material.

Here, the concentration step is performed at a concentration of 40 to 80 캜, a concentration of 0.0009 to 0.122 kgf / cm 2, and a concentration time of 6 to 24 hours.

Here, the enzyme treatment step is an enzyme treatment at an enzyme treatment temperature of 30 to 60 DEG C, a pH of 4 to 7.5, and an enzyme treatment time of 20 to 30 hours.

Here again, the enzyme is selected from the group consisting of Alcalase, Fructose, Termamyl, Cellubiose and combinations thereof.

Here, the pulverization process may be performed by supplying a predetermined amount of a dye to a spray dryer using a feed pump while stirring the dye with a stirrer, spraying the discrete droplets onto the diskette, adjusting the size and pulverization of the dye through rotation and temperature control of the diskette, The natural dye powder produced from the diskette is discharged through a primary cyclone, and the unreacted natural dye powder is transferred to a secondary cyclone through a bag filter and discharged.

Herein, the natural dyestuffs can also be used in a variety of colors such as Caesalpinia sappan L., Terminalia chebula Retzius, Punica granatum L., Rubia tinctorum L., Green tea (Camellia sinensis O.Kuntge) Chrysanthemum morifolium, Artemisia capillaris thunb, Sophora japonica L., Chamaecyparis obtusa S. et Z. ENDL., Lacquer, Dactylopius coccus costa, ), Persicaria tinctoria H. gross, Rheum undulatum L., Butea Frondosa, Vitis vinifera L., Robinia pseudoacacia L., Lawsonia inermis L., Uncaria gambir Roxburgh, Santalum album L, Kerria lacca, Logwood (Heamatoxylon campechianum) and combinations thereof.

According to the method for producing a natural dye for a dye-sensitized solar cell of the present invention having the above-described structure, natural dyes used for adsorbing natural dyes of a photoelectrode used in a dye-sensitized solar cell are extracted, concentrated, enzymatically treated, It is easy to store for a long period of time and can be easily used.

FIG. 1 is a process diagram for illustrating a method for producing a natural dye for a dye-sensitized solar cell according to the present invention.
2 is a photograph of a natural dye powder prepared according to Experimental Example of the present invention.
3 is a graph showing particle sizes of natural dye powders prepared according to Experimental Example of the present invention.

Hereinafter, a method for producing a natural dye for a dye-sensitized solar cell according to the present invention will be described in detail with reference to the accompanying drawings.

In the following description of the present invention, detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear. The following terms are defined in consideration of the functions of the present invention, and these may be changed according to the intention of the user, the operator, or the like. Therefore, the definition should be based on the contents throughout this specification.

FIG. 1 is a process diagram for illustrating a method for producing a natural dye for a dye-sensitized solar cell according to the present invention.

1, a method for producing a natural dye for a dye-sensitized solar cell according to the present invention comprises an extraction step (S100), a concentration step (S110), an enzyme treatment step (S120), and a pulverization step (S130) .

&Quot; Extraction process-S100 "

First, the cut natural salt is put into an extractor and extracted at a temperature of 30 to 98 ° C, an extraction pressure of 0.0007 to 0.122 kgf / cm 2, an extraction time of 30 to 130 minutes, and one or two times depending on the characteristics of the material.

&Quot; Concentration Process-S110 "

Then, the extract liquid extracted from the extractor is put into a concentrator and is concentrated at a concentration of 40 to 80 ° C, a condensation pressure of 0.0009 to 0.122 kgf / cm 2, and a concentration time of 6 to 24 hours.

&Quot; Enzyme treatment process-S120 "

When the preparation of the concentrate is completed, the enzyme is added to the concentrate, and the enzyme is treated at an enzyme treatment temperature of 30 to 60 ° C, a pH of 4 to 7.5, and an enzyme treatment time of 20 to 30 hours. Wherein the enzyme is selected from the group consisting of Alcalase, Fructose, Termamyl, Cellubiose and combinations thereof.

&Quot; Powdering process-S130 "

When the enzymatic treatment is completed, the enzyme-treated concentrate is pulverized. The dye is stirred by a stirrer, fed to a spray dryer by a feed pump, and sprayed on a diskette. The size of the dye through rotation and temperature control of the diskette And the natural dye powder produced from the diskette is discharged through the primary cyclone and the unreacted natural dye powder is transferred to the secondary cyclone through the bag filter and discharged. Here, the natural dyes are selected from the group consisting of Caesalpinia sappan L., Terminalia chebula Retzius, Punica granatum L., Rubia tinctorum L., Green tea (Camellia sinensis O.Kuntge), Chrysanthemum morifolium , Artemisia capillaris thunb, Sophora japonica L., Chamaecyparis obtusa (S. et Z.) ENDL., Lacquer, Dactylopius coccus costa, Indigo Persicaria tinctoria H. gross, Rheum undulatum L., Butea Frondosa, Vitis vinifera L., Robinia pseudoacacia L., Lawsonia inermis L., Uncaria gambir Roxburgh, Santalum album L, Kerria lacca, Logwood (Heamatoxylon campechianum), and combinations thereof.

&Quot; Experimental Example &

○ Callus (Caesalpinia sappan L.)

- Salt description

ㅇ A plant that grows in the tropics with small thorns in the number of 5 ~ 9m in height

ㅇ The small brow is gray-green, the leaf is double-headed, the post is opposite,

ㅇ Yellow flowers bloom in May-June and fruit is born in September-October

- Color and characteristics: Dihydropyran dyestuffs Dyes of brazilin color and many benzene structures

- Extraction, concentration, enzyme treatment process

- Article Photos

○ Gaza (Terminalia chebula Retzius)

- Salt description

ㅇ Deciduous tree belonging to the family

ㅇ The new branch is yellowish brown with brown hairs at 25m in height. Leaves are alternate and thick

ㅇ Flowers are yellow with green color, calyx has 5 ends, and 10 stamens come out of calyx.

ㅇ The fruit used as medicinal material is egg-shaped and egg-shaped. Outer side is yellowish brown to brownish shine. There are five prominent wrinkles vertically and irregular wrinkles therebetween.

- Color and Characteristics: It is used for extracting yellow cow called myrovalan. Yellow meringue for Al mulling, Gray for Fe mordering

- Extraction, concentration, enzyme treatment process

* Secondary extraction was carried out at 98 ° C for 24 hours and the concentration conditions were the same.

- Article Photos

○ Green tea (Camellia sinensis O.Kuntge)

- Salt description

ㅇ The primary goal of green tea production, which is mainly consumed in Asia, is the preservation of catechins present in tea

ㅇ Inactivation of oxidizing enzymes in the process of preservation prevents the oxidation of polyphenol components, thus maintaining the content of raw leaves

ㅇ Green tea was first produced and used in China and India. Nowadays,

- Color and Characteristic: High coloring of silk fiber is observed. Y chromaticity of color increases as the mordant concentration of Fe and Y increase.

- Extraction, concentration, enzyme treatment process

- Article Photos

○ Chrysanthemum morifolium

- Salt description

ㅇ The lower part of the stem is ligneous with a height of about 1m, the leaves are alternate,

ㅇ Flowers are flowers with a flower at the end of the stem.

ㅇ Flower color varies according to varieties such as yellow, white, red, purple, and size and shape are different.

ㅇ The varieties are classified as small, medium, and large.

- Color and characteristics: It is a dyeing color of yellow system, it is comparatively excellent in fastness. Antimicrobial and deodorant are most excellent in Cu mildew

- Extraction, concentration, enzyme treatment process

- Article Photos

○ Artemisia capillaris thunb

- Salt description

ㅇ By using the outpost, it is usually used when the flower starts to bloom.

ㅇ Dyeing with light yellow-green color, slightly brown when stained by Al mingling, collected in March to May

ㅇ The color becomes darker as the collection time is delayed.

- Colors and characteristics: Using mugwort collected in June, it is dyed with a deep yellow color. Using mugwort collected in July and August, it starts to brown. After September, its color becomes lighter.

- Extraction, concentration, enzyme treatment process

- Article Photos

○ Pomegranate (Punica granatum L.)

- Salt description

O Origin is located in West Asia and northwest of India.

ㅇ All muscle, bark, and peel are isopelletierine,

- Color and Characteristic: It is mainly used as a dyestuff as a dyestuff; as a brown type dye, it is yellow by Al mordant, blackish brown by Fe mordant, it is dyed with mordant brown in combination with Fe and alkali, and ellagic aced Mainly borne by

- Extraction, concentration, enzyme treatment process

- Article Photos

- Dye powdering process using spray dryer

1. Keep the first concentrated dye out of precipitation through an agitator.

2. Supply the dye in the agitator to the spray drier by a certain amount through the feed pump.

3. Control the size and pulverization of the dye by rotating the diskette and adjusting the temperature. At this time, since the dye is adhered to the wall of the spray dryer by the centrifugal force of the diskette, it is prevented by controlling the temperature and rotation speed of the sweeper. Also, the diskette is used at a rotation speed of 5,000 ~ 20,000 rpm, but the rpm value of the equipment operation efficiency and natural dye powdering is 9,000 ~ 12,000 rpm.

4. The produced dye powder is discharged through the primary cyclone, and the dye powder that is discharged is moved to the secondary cyclone through the bag filter and discharged.

5. The temperature of the inlet and outlet of the spray dryer is an important part of the powdering process of natural dyestuffs. Depending on the temperature, a lump of powder or mucilage is formed. The rising temperature of the inlet side is the optimum drying temperature of the material to be dried. The inlet temperature is about 195 to 230 ° C, and the outlet temperature is generally maintained at 80 to 120 ° C and maintained at 90 to 115 ° C in this process. In addition, the pulverization process of natural dyes is determined depending on the kind of the salt, and whether or not the powder can be pulverized. The salt which is difficult to be pulverized is pulverized by using auxiliary additives (such as guar gum) after dye extraction. In general, the salt composed of a lot of tannin components, roots and trees is easy to be pulverized, and petals and other parts of the salt can be pulverized by using auxiliary additives.

2 is a photograph of a natural dye powder prepared according to Experimental Example of the present invention.

○ Analysis (GC / MS) results of lacquered prototype for natural dyes

- The component analysis (GC / MS) of the lacquered prototype for natural dyes is shown in the following Tables 2 and 3, and the active ingredient to be measured in this experiment is not measurable

- Judged by the difference in the content of the sample in the measurement and the measurement difference in the gas chromatography.

- need to analyze under additional conditions

○ Nano particle size analysis of natural pigment

- Sample name: Izukal Nano

- Color: Ivory color

- Instrument name: Particle size analyzer

3 is a graph showing particle sizes of natural dye powders prepared according to Experimental Example of the present invention.

○ Results of particle size analysis

- Izolite nanoparticles are distributed in various sizes between 100nm and 450nm as shown in the figure above.

- It is judged that the graph is widely measured because the dispersion of the sample is not smooth and the uniformity of the particles is low.

- Further development required for particle uniformity

○ Functional Analysis: Selecting samples with high stability in external conditions such as light and temperature,

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. It is to be understood, however, that the invention is not to be limited to the specific forms thereof, which are to be considered as being limited to the specific embodiments, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims. .

Claims (7)

An extracting step of adding a natural salt to an extractor and extracting it under a predetermined condition;
A concentrating step of putting the extract liquid extracted from the extractor into a concentrator and concentrating the concentrate under a predetermined condition;
An enzyme treatment step in which an enzyme is added to a concentrate; And
And a pulverizing step of pulverizing the enzyme-treated concentrate into powder. The method for producing a natural dye for a dye-sensitized solar cell according to claim 1, The method according to claim 1,
In the extraction step,
Wherein the extraction is carried out at a temperature of 30 to 98 ° C, an extraction pressure of 0.0007 to 0.122 kgf / cm 2, an extraction time of 30 to 130 minutes, and one to two times depending on the characteristics of the material. The method according to claim 1,
In the concentration step,
Wherein the concentrating step is performed at a concentration of 40 to 80 캜, a concentration of 0.0009 to 0.122 kgf / cm 2, and a concentration time of 6 to 24 hours. The method according to claim 1,
The enzyme treatment process may comprise:
Wherein the enzymatic treatment is carried out at an enzyme treatment temperature of 30 to 60 DEG C, a pH of 4 to 7.5, and an enzyme treatment time of 20 to 30 hours for enzymatic treatment. The method according to claim 1,
Preferably,
Wherein the organic dye is selected from the group consisting of Alcalase, Fructose, Termamyl, Cellubiose, and combinations thereof. The method according to claim 1,
In the pulverizing step,
The dyestuff is mixed with a stirrer and fed to the spray drier by a feed pump to spray the discrete droplets on the diskette. The size and the powdering of the dyestuff are controlled by controlling the rotation and temperature of the diskette. Wherein the natural dye powder is discharged through a primary cyclone, and the natural dye powder which is not discharged is transferred to a secondary cyclone through a bag filter and discharged. The method according to claim 1,
The natural dyes include,
(Caesalpinia sappan L.), Terminalia chebula Retzius, Punica granatum L., Rubia tinctorum L., Green tea (Camellia sinensis O.Kuntge), Chrysanthemum morifolium, Artemisia capillaris thunb), Sophora japonica L., Chamaecyparis obtusa (S. et Z.) ENDL., Lacquer, Dactylopius coccus costa, Persicaria tinctoria H. gross, , Ruthum undulatum L., Butea Frondosa, Vitis vinifera L., Robinia pseudoacacia L., Lawsonia inermis L., Uncaria gambir Roxburgh, Wherein the dye is selected from the group consisting of Santalum album L, Kerra lacca, Logwood (Heamatoxylon campechianum), and combinations thereof.

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