KR101648001B1 - Pyridinium salt-bound nano-particles, prepration method thereof and nanogel-type electrolyte using the same - Google Patents

Abstract

The present invention discloses surface-modified nanoparticles, a method for producing the same, and a nanogel-type electrolyte containing the same.
The surface-modified nanoparticles according to the present invention, the method for producing the nanoparticles, and the nanogel-type electrolyte comprising the nanoparticles according to the present invention include the pyridinium salt-bound nanoparticles represented by Chemical Formula 1, It is possible to form an electrolyte layer by printing and advantageous in mass production and it is possible to lower the concentration of ionic liquid in the electrolyte because it contains an ionic liquid system material, The efficiency of the dye-sensitized solar cell can be improved.

Description

TECHNICAL FIELD The present invention relates to a nanoparticle-modified nanoparticle, a method for producing the same, and a nanogel-type electrolyte containing the same.

The present invention relates to a surface-modified nanoparticle, a method for producing the same, and a nano-gel electrolyte including the same. More particularly, the present invention relates to a nanoparticle- Surface-modified nanoparticles that can improve the efficiency of dye-sensitized solar cells, and a method for producing the same, which can improve the efficiency of the dye-sensitized solar cell, can reduce the concentration of the ionic liquid system in the electrolyte, And a nano-gel electrolyte containing the same.

Recently, serious environmental pollution problem and depletion of fossil energy are increasing importance for next generation clean energy development. Among them, solar cells convert solar energy directly into electrical energy. It is expected to be an energy source capable of solving future energy problems because it has fewer pollution, has infinite resources and has a semi-permanent lifetime. Such solar cells are divided into inorganic solar cells, dye-sensitized solar cells, and organic solar cells. Monocrystalline silicon is mainly used as an inorganic solar cell. Such a monocrystalline silicon solar cell has advantages that it can be manufactured by a thin film solar cell, but it is expensive and low in stability.

In addition, the dye-sensitized solar cell uses a liquid electrolyte to raise the problem of stability of the battery module. Particularly, the liquid electrolyte is difficult to seal, and there is a problem of electrolyte volatilization or leakage due to an increase in external temperature. In order to solve this problem, there have been problems such as lack of chemical stability, and inorganic solid electrolytes and polymer solid electrolytes instead of liquid electrolytes have been developed. However, when such solid electrolytes are used, the interface transfer characteristics of electrons and ions are poor, Solid state "or" solid-state " state through the production of a gel electrolyte using an ionic liquid in order to improve the photoelectric conversion efficiency of such a non-liquid electrolyte, state "dye-sensitized solar cell has been actively developed. In a previously published paper [Journal of Fluorine Chemistry Volume 125 (August 2004), Pages 1241-1245], studies have been published on nano-gel electrolytes mixed with nanosilica materials and liquid electrolytes. The gel electrolyte prepared by mixing the nanosilica material and the liquid electrolyte disclosed in the above paper has a disadvantage in that the affinity between the nanosilica and the liquid electrolyte is poor and the liquid electrolyte easily evaporates at a high temperature. Of the population.

Furthermore, in addition to the above-described solar cell, a device using an electrolyte such as a lithium battery, a fuel cell, or a super capacitor as a technical element still has the same problem.

Therefore, the first technical problem to be solved by the present invention is to provide an electrostatic image forming apparatus capable of forming an electrolyte layer by printing and advantageous in mass productivity, To thereby reduce the production cost, and to provide surface-modified nanoparticles that can improve dye-sensitized solar cell efficiency in particular.

The second technical problem to be solved by the present invention is to improve the long-term stability, and it is possible to form an electrolyte layer by printing, which is advantageous in mass production, and contains an ionic liquid system material, The present invention also provides a method for preparing nanoparticles having surface modified nanoparticles which can improve the efficiency of dye-sensitized solar cells.

In addition, the technical problem to be solved by the present invention is to improve the long-term stability, and it is possible to form an electrolyte layer by printing, which is advantageous in mass production, and contains an ionic liquid system material, thereby lowering the ionic liquid system concentration in the electrolyte And to provide a nano-gel electrolyte which can be expected to reduce the production cost and thus improve the efficiency of the dye-sensitized solar cell.

In order to solve the first technical problem described above, the present invention provides a pyridinium salt-bound nanoparticle represented by the following general formula (1).

≪ Formula 1 >

(NP: nanoparticle, R: alkyl iodide)

According to an embodiment of the present invention, the pyridinium salt may be a salt in which an alkyl iodide represented by the following general formula (2) is reacted.

(2)

C _n H _{2n + 1} I, n = 1 to 15 (C: carbon, H: hydrogen n: integer)

According to another embodiment of the present invention, the NP is a particle having an average particle diameter of nanoscale (nm), and may be silica (SiO ₂ ), titania (TiO ₂ ) or tin oxide (SnO ₂ ) have.

According to another aspect of the present invention, there is provided a nanoparticle-containing solution containing nanoparticles dispersed in an organic solvent, wherein the nanoparticle solution is loaded with 2- (4-pyridylethyl) triethoxysilane and refluxed. A step S2 of washing and drying the powder obtained by filtration to prepare a precursor powder, and a step S3 of mixing and reacting the precursor powder with an alkyl iodide solution, followed by drying. do.

delete

According to another embodiment of the present invention, the alkyl iodide solution may be a mixture of the alkyl iodide represented by Formula 2 and a polar solvent.

(2)

C _n H _{2n + 1} I, n = 1 to 15

(C: carbon, H: hydrogen n: integer)

In order to solve the third technical problem, the present invention provides a nano-gel electrolyte in which the nanoparticles and the liquid electrolyte are mixed.

According to an embodiment of the present invention, the liquid electrolyte may include an ionic liquid and an oxidation-reduction derivative.

According to another embodiment of the present invention, the ionic liquid is selected from the group consisting of n-methylimidazolium iodide, n-ethylimidazolium iodide, ethyl-methylimidazolium iodide, 1-benzyl- Ethyl-3-methylimidazolium iodide, 1-butyl-3-methylimidazolium iodide, methylpyridinium iodide, ethylpyridinium iodide, propylpyridinium iodide, methylethylpyrrolidinium iodide, Or a mixture of at least one member selected from the group consisting of dimethylpyrrolidinium iodide, ethylmethylimidazolium dicyanamide and guanidinium thiocyanate.

According to another embodiment of the present invention, the oxidation-reduction derivative is selected from the group consisting of lithium iodide, sodium iodide, potassium iodide, lithium bromide, sodium bromide, potassium bromide, quaternary ammonium salt, imidazolium salt and pyridinium salt Lt; / RTI >

According to the present invention, it is possible to form an electrolyte layer by printing with advantage of long-term stability improvement, and it is advantageous in mass productivity, and it is possible to lower the ionic liquid system concentration in the electrolyte because it contains ionic liquid system material, It is possible to expect a reduction in the unit cost, and in particular, the efficiency of the dye-sensitized solar cell can be improved.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a process flow chart showing a method for producing nanoparticles modified with a surface according to the present invention. FIG.

These and other objects, features and other advantages of the present invention will become more apparent by describing in detail preferred embodiments of the present invention with reference to the accompanying drawings. Hereinafter, a surface-modified nanoparticle according to an embodiment of the present invention, a method for producing the nanoparticle, and a nanogel-type electrolyte including the same will be described in detail with reference to the accompanying drawings.

The nanoparticles according to the present invention are characterized in that a pyridinium salt represented by the following formula (1) is bonded.

≪ Formula 1 >

(NP: nanoparticle, R: alkyl iodide)

The pyridinium salt is prepared by reacting pyridine with a surface-modified nanoparticle and an alkyl iodide with a silane-based nanoparticle coupling agent such as 2- (4-pyridylethyl) triethoxysilane.

The nanoparticles have a nano-scale size. The nanoparticles have an average particle size of about 7 to 100 nm. In the present invention, silica (SiO ₂ ), titania (TiO ₂ ), or tin Oxide (SnO ₂ ) particles can be used.

The pyridinium salt may be a salt in which an alkyl iodide represented by the following general formula (2) is reacted. When the number of carbon atoms is more than 15, the ion conductivity of the electrolyte is reduced, Can be adversely affected.

(2)

C _n H _{2n + 1} I, n = 1 to 15 (C: carbon, H: hydrogen n: integer)

Meanwhile, the method for producing nanoparticles modified with a surface according to the present invention comprises: S1 step of adding 2- (4-pyridylethyl) triethoxysilane to a nanoparticle-containing solution in which the nanoparticles are dispersed in an organic solvent and refluxing the solution; A step S2 of washing and drying the obtained powder to prepare a precursor powder and a step S3 of mixing and reacting the precursor powder with an alkyl iodide solution and drying the powder. (4-pyridylethyl) triethoxysilane is added to a solution in which nanoparticles are dispersed in an organic solvent to reflux the organic solvent. The organic solvent can be used without limitation within a range of uniform dispersion of the nanoparticles, A separate dispersant may be used.

The nanoparticles may be silica (SiO ₂ ), titania (TiO ₂ ), or tin oxide (SnO ₂ ) particles having an average particle diameter of about 7 to 100 nm. The reflow process of the present process may use a coupling agent The surface modification of the nanoparticles is effectively performed.

delete

Next, in step S2, the powder obtained by filtration of the refluxed solution is washed and dried to prepare a precursor powder. The surface-modified nanoparticles are washed and dried so as to obtain the dried product. If the temperature is lower than 200 ° C, the cleaning solvent may remain. On the other hand, if the temperature exceeds 300 ° C, deformation of the material synthesized by heat may be caused.

Next, in step S3, the precursor powder and the alkyl iodide solution are mixed, reacted and dried. In order to efficiently and uniformly mix the precursor powder with the alkyl iodide solution, the alkyl iodide solution The solvent may be a polar solvent such as acetonitrile.

Meanwhile, the gel-type electrolyte according to the present invention includes the above-mentioned pyridinium salt as a mixture of the surface-modified nanoparticles and the liquid electrolyte.

In addition, the liquid electrolyte may include an ionic liquid and an oxidation-reduction derivative. Examples of the ionic liquid include n-methylimidazolium iodide, n-ethylimidazolium iodide, ethyl-methylimidazolium iodide, Ethyl-3-methylimidazolium iodide, 1-butyl-3-methylimidazolium iodide, methylpyridinium iodide, ethylpyridinium iodide, propylpyridinium iodide, At least one selected from the group consisting of iodine, iodine, iodine, iodine, iodine, methylethylpyrrolidinium iodide, dimethylpyrrolidinium iodide, ethylmethylimidazolium dicyanamide and guanidinium thiocyanate, At least one selected from the group consisting of lithium iodide, sodium iodide, potassium iodide, lithium bromide, sodium bromide, potassium bromide, quaternary ammonium salts, imidazolium salts and pyridinium salts Can be used.

Preparation Example 1 Preparation of surface-modified nanoparticles

To a solution of 5 g of silica nanoparticles (Aerosil, average particle diameter 12 nm) dispersed in 100 ml of toluene in a nitrogen atmosphere, a solution of 1 g of 2- (4-pyridylethyl) triethoxysilane dispersed in 2 ml of toluene was dropwise added dropwise at 80 ° C. for 18 hours The powder obtained by filtration was washed with ethanol and acetone and then dried in a vacuum oven at 250 ° C for 24 hours to obtain a precursor powder. Then, a solution of 2 ml of 1-iodohexane dissolved in 25 ml of acetonitrile was added dropwise to 5 g of the precursor powder, and the mixture was stirred at room temperature for 1 hour. The powder was then evaporated by rotary evaporation at 60 ° C, washed with diethyl ether and ethanol, And dried in a vacuum oven for 24 hours to prepare nanoparticles whose surface was modified.

Preparation Example 2 Preparation of surface-modified nanoparticles

The surface-modified nanoparticles were prepared in the same manner as in Preparation Example 1, except that 1-iodooctane was used in place of 1-iodohexane.

Preparation Example 3 Preparation of surface-modified nanoparticles

Surface modified nanoparticles were prepared as in Preparation Example 1 except that 1-iododecane was used instead of 1-iodohexane.

Example 1

0.6 g of surface modified nanoparticles according to Preparation Example 1 and 0.6 g of an electrolyte (3-Methoxy propionitrile + LiI (0.1 M) + I 2 (0.05 M) + 1-Butyl-3-methylimidazolium iodide (0.5 M)) were mixed to prepare a nano-gel electrolyte.

Example 2

0.6 g of the surface-modified nanoparticles prepared in Preparation Example 2 and 0.6 g of the electrolyte (3-Methoxy propionitrile + LiI (0.1 M) + I 2 (0.05 M) + 1-Butyl-3-methylimidazolium iodide (0.5 M)) were mixed to prepare a nano-gel electrolyte.

Example 3

0.6 g of the surface-modified nanoparticles prepared in Preparation Example 3 and 0.6 g of the electrolyte (3-Methoxy propionitrile + LiI (0.1 M) + I 2 (0.05 M) + 1-Butyl- 3-methylimidazolium iodide (0.5M)) were mixed to prepare a gel-type electrolyte.

Comparative Example 1

A gel electrolyte was prepared in the same manner as in Example 1 except that a conventional nano gel (trade name, product name) was used.

Comparative Example 2

A gel electrolyte was prepared in the same manner as in Example 1 except that a conventional liquid electrolyte (company name, product name) was used.

Experimental Example 1

In order to evaluate the characteristics of the gel electrolyte according to the present invention, a dye-sensitized solar cell including a sieve electrolyte was prepared and evaluated as follows.

A transparent glass substrate on which a fluorine-doped tin oxide transparent conductive oxide layer was formed was prepared, and a coating composition containing titanium dioxide was coated on the transparent conductive oxide layer by a doctor blade method and heat-treated at 500 ° C for 30 minutes An oxide layer having a thickness of 8 占 퐉 was formed. Next, a coating composition containing titanium dioxide was applied onto the oxide layer by a doctor blade method, and heat treatment was performed at 500 ° C. for 30 minutes to form an oxide layer having a thickness of 15 μm. Then, 0.2 nM ruthenium dithiocyanate 2,2'-bipyridyl-4,4'-dicarboxylate dye solution was prepared, and the substrate on which the oxide layer was formed was carried thereon for 24 hours and dried A negative electrode having a dye adsorbed thereon was prepared. Further, a transparent glass substrate on which a fluorine-doped tin oxide transparent conductive oxide layer was formed was prepared, and a 2-propanol solution in which hydrogenated chloroplatinic acid (H ₂ PtCl ₆ ) was dissolved was dropped on the transparent conductive oxide layer. Lt; 0 > C for 30 minutes to prepare a positive electrode having a platinum layer formed thereon. Next, a gel electrolyte according to Example 1 was applied to the top of the negative electrode, and the positive electrode was disposed to face the positive electrode, and a thermoplastic polymer layer having a thickness of about 60 mu m made of SURLYN (Du Pont) And then placed in an oven at 130 캜 for 2 minutes to prepare a dye-sensitized solar cell, and the light conversion efficiency thereof was evaluated. In this experiment, photovoltaic and photocurrent were measured by measuring the photocurrent and the photocurrent in the following manner, and the photocurrent was measured using the current density (I _sc ), the voltage (V _oc ), and the fill factor (ff) The conversion efficiency (? _E ) was calculated by the following equation (1). At this time, a Xenon lamp (Oriel) was used as a light source, and the solar condition (AM 1.5) of the Xenon lamp was corrected using a standard solar cell.

&Quot; (1) "

? _e = (V _oc x I _sc x ff) / (P _ine )

In Equation (1), (P _ine ) represents 100 mW / cm 2 (1 sun).

Experimental Examples 2 to 5

Experimental Examples 2 to 5 were prepared in the same manner as in Example 1 except that the gel electrolyte of Experimental Example 1 was used instead of the electrolyte of Examples 1 to 3 and Comparative Examples 1 and 2 to evaluate the properties of the dye- (In the case of the liquid electrolyte of Comparative Example 2, a liquid injection port was formed as in the conventional method, and then an electrolyte was injected and sealed and processed)

Experimental evaluation

The evaluation results of Experimental Examples 1 to 5 are shown in Table 1 below.

division Current density (mA) Voltage (V) Fill factor Light conversion efficiency (%) Experimental Example 1 13.1 0.74 0.73 7.03 Experimental Example 2 13.0 0.73 0.73 6.93 Experimental Example 3 12.9 0.74 0.73 6.97 Experimental Example 4 11.9 0.70 0.74 6.14 Experimental Example 5 12.8 0.73 0.73 6.82

Referring to Table 1, the dye-sensitized solar cell using the gel electrolyte according to the embodiment of the present invention has a higher current density than the conventional silica nanogel (Experimental Example 4) and liquid electrolyte (Experimental Example 5) , It can be confirmed that the light conversion efficiency is improved. Therefore, the gel electrolyte according to the present invention has advantages of improving long-term stability, and it is possible to form an electrolyte layer by printing, which is advantageous in mass productivity, and can contain an ionic liquid system material, thereby lowering the ionic liquid system concentration in the electrolyte, Accordingly, the production cost can be reduced, and the efficiency of the dye-sensitized solar cell can be improved.

Claims (12)

delete delete delete Step (S1) of adding 2- (4-pyridylethyl) triethoxysilane to a nanoparticle-containing solution in which nanoparticles of Formula 1 are dispersed in an organic solvent and refluxing the solution;
Filtering the refluxed solution, washing and drying the obtained powder to prepare a precursor powder; And
And mixing the precursor powder and the alkyl iodide solution, followed by reaction and drying.
[Chemical Formula 1]

(NP: nanoparticle, R: alkyl iodide)
delete delete 5. The method of claim 4,
Wherein the alkyl iodide solution is a mixture of the alkyl iodide represented by Formula 2 and a polar solvent.
[Chemical Formula 2]
C _n H _{2n + 1} I, n = 1 to 15
(C: carbon, H: hydrogen n: integer)
A nanoparticle modified according to claim 4 or 7.
A nano-gel electrolyte in which the surface-modified nanoparticles of claim 8 and a liquid electrolyte are mixed.
10. The method of claim 9,
Wherein the liquid electrolyte comprises an ionic liquid and an oxidation-reduction derivative.
11. The method of claim 10,
The ionic liquid may be selected from the group consisting of n-methylimidazolium iodide, n-ethylimidazolium iodide, ethyl-methylimidazolium iodide, 1-benzyl- Methyl iodide, iodine, iodine, iodine, iodine, iodine, iodine, iodine, iodine, iodine, Methyl imidazolium dicyanamide, and guanidinium thiocyanate. 2. The nano-gel electrolyte according to claim 1,
11. The method of claim 10,
The oxidation-reduction derivative is at least one selected from the group consisting of lithium iodide, sodium iodide, potassium iodide, lithium bromide, sodium bromide, potassium bromide, quaternary ammonium salt, imidazolium salt and pyridinium salt. Electrolyte.

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