CN103871746B - A kind of sensitization solar battery based on different shape nanogold - Google Patents
A kind of sensitization solar battery based on different shape nanogold Download PDFInfo
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Abstract
The present invention relates to sensitization solar battery, a kind of sensitization solar battery based on different shape nanogold is refered in particular to；The sensitizer of this solar cell by two kinds of different shapes nanogold（It is spherical and bar-shaped）Composition, excites the surface plasma primitive of lower generation to resonate and injects electrons into the semiconductor of light anode using these nanogold in light（Such as TiO2, ZnO etc.）In, so as to produce photoelectric effect；Because the optical absorption band of different shape nanogold is different, the photoresponse ability and energy conversion efficiency for being provided simultaneously with the sensitization solar battery of a variety of different shape nanogold are higher than the solar cell of single form nanogold sensitization；Present invention is disclosed a kind of method for improving metal cluster sensitization solar battery light utilization ratio, have great importance to area of solar cell.
Description
Technical field
The present invention relates to sensitization solar battery, a kind of sensitization solar battery based on different shape nanogold is refered in particular to.
Background technology
1991, O ' Regan and Gr tzel reported the first DSSC, and its energy conversion efficiency is
7%；So far, the sensitization solar battery efficiency based on different electrolyte and sensitizer has broken through 11%, but its it is practical still according to
Rely the breakthrough of following two aspects：Higher energy conversion efficiency（~15%）With more preferable stability；Short-circuit photocurrent（J sc）It is
One of key factor of sensitization solar battery efficiency is influenceed, it is mainly by sensitizer（Dyestuff, quantum dot, metal etc.）Captured
The quantity and electronics of luminous energy transport decision in light anode semiconductor；It is generally concentrated at for the research for improving short-circuit photocurrent
New dyestuff design and develop aspect because light absorbs of the N719 dyestuffs being widely used in 600-750 nm wave-length coverages
It is weaker, and had more than in AM 1.5 sunshine 60% energy be in 600 nm wavelength more than in the range of；At present, energy turns
Change the leading DSSC of efficiency and employ new dye, including original sensitizer improvement and to-acceptor
Substituted porphyrin sensitizer（Donor–Acceptor Substituted Porphyrin）Deng；However, these dye class are sensitized
Agent is generally under light illumination, particularly under the illumination containing ultraviolet and unstable, is that the performance of DSSC exists
One of the reason for being deteriorated in short period.
2013, Kamat etc. reported a kind of solar cell of gold nano cluster sensitization, and its operation principle is nanogold
Light is excited, and injects electrons into light anode TiO2In, so as to form photoelectric current；Because sensitizer is gold nano cluster rather than dye
Material, therefore this sensitized cells are expected to the problem of solution sensitizer is decomposed under light illumination, so as to improve the stability of battery；So
And, due to the gold nano cluster using single form, the photo absorption property of this sensitized cells is not good, and its photoresponse wavelength is about
In 550 below nm, therefore it is unfavorable for making full use of sunshine and the further energy conversion efficiency of raising battery.
The problem of present invention exists for the battery of the reports such as Kamat, proposes quick altogether using two kinds of different shape nanogold
The method of change improves the photo absorption property and energy conversion efficiency of metal nanometer cluster sensitization solar battery, and this method
Have no patent or non-patent literature report.
The content of the invention
It is an object of the invention to overcome the shortcomings and deficiencies that above-mentioned prior art is present, a kind of new nanogold is developed
Sensitization solar battery.
The preparation method of nanogold sensitization solar battery proposed by the present invention comprises the following steps：
1）Prepare light anode：Certain thickness TiO is prepared on transparent conducting glass electrode first2Stratum granulosum or TiO2Receive
Rice rod layer, then calcines to obtained electrode, finally carries out TiCl4Processing.
2）Prepare the colloidal solution of gold nanorods：First, with HAuCl4•3H2O is as golden presoma, with cetyl three
Methyl bromide ammonium prepares nanogold kind using sodium borohydride as reducing agent as surfactant；Then, with HAuCl4 3H2O
As the presoma of gold, using cetyl trimethylammonium bromide as surfactant, using ascorbic acid as reducing agent, and profit
Gold nanorods are grown with the nanogold kind and silver nitrate of above-mentioned preparation, finally unnecessary surface-active are removed using the method for centrifugation
Agent, and gold nanorods are dispersed in water obtain gold nanorods colloidal solution it is standby.
3）The sensitization of light anode：First, by step 1）The light anode of middle preparation is dipped into certain density and pH value
HAuCl4•3H2In the O aqueous solution, it is put into Muffle furnace and calcines after light anode is taken out after certain time, being cleaned with water, so as to prepare
The light anode of spherical nanogold sensitization；Then, the light anode spherical nanogold of above-mentioned preparation being sensitized is immersed in 3- sulfydryls third
Surface modification is carried out in the aqueous solution of acid, then the light anode after modification is immersed in step 2）The gold nanorods dispersion liquid of middle preparation
In, take out after light anode, cleaning-drying that the spherical and golden light anode being sensitized altogether of rod-like nano is made after immersion（Such as Fig. 1 institutes
Show）.
4）Prepare to electrode：By H2PtCl6•3H2O aqueous isopropanol is coated on the transparent conducting glass punched in advance
On, calcined after being put into after solvent volatilization in Muffle furnace.
5）The assembling of battery：By step 3）The nanogold sensitization light anode and step 4 of preparation）What is prepared uses certain to electrode
The sarin film of thickness is bonded under conditions of heating, then by electrolyte by being injected into light sun to the aperture on electrode
In pole, the space constituted to electrode and sarin film, finally battery is completed to being sealed to the aperture on electrode with sarin film
Assembling（As shown in Figure 2）.
The step 1）Middle TiO2The preparation method of light anode is but is not limited to rubbing method or hydro-thermal reaction method.
The rubbing method is used to prepare granular TiO2Light anode：First by TiO2Nano particle is added to containing surface
In the mixed solvent of activating agent；Then ultrasound and stirring, the muddy for making it be creamy white are carried out to solution；
Then uniform TiO is formed in the conductive glass surface of cleaning with medicator2Pulp layer；Finally treat that solvent is evaporated completely
It is put into Muffle furnace and calcines after finishing；Finally carry out TiCl4Processing.
The TiO2Nano particle is not particularly limited, and its granular size is preferably 20 nm to 100 nm.
The mixed solvent contains but is not limited to water, ethanol and acetic acid, and the volume ratio of its reclaimed water and ethanol is preferably 1/3 ~
4/5：1, the volume ratio of acetic acid and ethanol is preferably 1/20 ~ 1/5；1, TiO2Mass percent of the nano particle in mixed solvent
Preferably 5% to 15%.
The surfactant include but is not limited to Triton X-100, Triton X-102, Triton X-114 and
Nonionic surface active agent including Triton X-165, its mass percent in mixed solvent be preferably 0.1% to
3%。
The TiCl4Processing is that the electrode after calcining is put into 70 °C of TiCl4The aqueous solution（40 mM）In 30 minutes, so
Cleaned afterwards with pure water, place into and calcine 30 min in Muffle furnace under 450 °C.
The rubbing method can be repeated several times in same conductive glass surface, so as to increase TiO2The thickness of nano-particle layer,
The TiO2The thickness of nano-particle layer is not particularly limited, preferably 5 μm to 20 μm.
The hydro-thermal reaction method is used to prepare TiO2Nanometer rods light anode：The electro-conductive glass of cleaning is placed in containing metatitanic acid four
In the reactor of the aqueous hydrochloric acid solution of N-butyl, TiO is grown in conductive glass surface by hydro-thermal reaction2Nanometer stick array,
Then electrode is calcined and TiCl4Processing.
The concentration of hydrochloric acid is preferably 10 wt% to 30 wt% in the aqueous hydrochloric acid solution.
Mass percent of the tetra-n-butyl titanate in aqueous hydrochloric acid solution is preferably 0.1 wt% to 5 wt%.
The hydrothermal reaction condition is that closed reactor is put into 150 C baking oven to react 20 h.
The calcine technology is that 30 min are calcined in 450 °C of Muffle furnace.
The TiCl4Handle and refer to the TiCl that the electrode after calcining is put into 70 °C4The aqueous solution（40 mM）In 30 minutes, so
Cleaned afterwards with pure water, place into and calcine 30 min in Muffle furnace under 450 °C.
The TiO2The length and diameter of nanometer rods are not particularly limited, and are respectively preferably 3 μm to 12 μm and 0.2 μm to 1
μm；Thickness is the length of rod.
The step 2）The preparation of middle nanogold kind is first by HAuCl4•3H2The O aqueous solution and cetyl trimethyl bromine
Change aqueous ammonium to be mixed, sodium borohydride aqueous solution is then rapidly added thereto, and be stirred vigorously, finally will be above-mentioned
Solution is put into 25 °C of water-baths and is aged 2 h.
The HAuCl4•3H2The concentration of the O aqueous solution is 0.01 M.
The concentration of the cetyl trimethylammonium bromide aqueous solution is 0.1 M.
The concentration of the sodium borohydride aqueous solution is 0.01 M.
HAuCl4•3H2The volume ratio of the O aqueous solution, the cetyl trimethylammonium bromide aqueous solution and sodium borohydride aqueous solution
For：0.25：7.5：0.6.
The step 2）The preparation of middle gold nanorods is by HAuCl4•3H2The O aqueous solution, silver nitrate aqueous solution and ascorbic acid
The aqueous solution is added sequentially in the cetyl trimethylammonium bromide aqueous solution and is well mixed, and then adds the nanometer prepared
Gold plants solution, finally stands overnight.
The HAuCl4•3H2The concentration of the O aqueous solution is preferably 0.002 M to 0.1M.
The concentration of the silver nitrate aqueous solution is 0.01 M.
The concentration of the aqueous ascorbic acid is 0.1 M.
The concentration of the cetyl trimethylammonium bromide aqueous solution is preferably 0.01 M to 0.2 M.
The mass percent of the nanogold kind GOLD FROM PLATING SOLUTION is about 5.9 × 10−3%。
HAuCl4•3H2The O aqueous solution, silver nitrate aqueous solution, aqueous ascorbic acid, cetyl trimethylammonium bromide are water-soluble
The volume ratio of liquid and nanogold kind solution is：1：015：0.16：23.75：0.02-0.2.
The average length and diameter of the gold nanorods are not particularly limited, and are respectively preferably 20 nm to 500 nm and 5 nm
To 50 nm.
The step 3）Middle HAuCl4•3H2The concentration of the O aqueous solution is preferably 0.001 M to 0.1 M, and its pH value is preferably
4.5 to 10, soak time is 8 h.
The step 3）In calcining heat be preferably 200 °C to 450 °C, calcination time be 2 h.
The step 3）In the average grain diameter of spherical nanogold that is formed on TiO2 surfaces be not particularly limited, preferably 1
Nm to 15 nm.
The step 3）The concentration of the middle 3- mercaptopropionic acids aqueous solution is preferably 0.01 M to 1.0 M.
The step 3）Golden concentration is not particularly limited in the aqueous dispersions of middle gold nanorods, and its mass percent is preferably
0.001% to 0.04%.
The step 4）In be to the painting method of electrode but be not limited to drop coating or spin coating.
The step 4）Middle H2PtCl6•3H2Mass percents of the O in aqueous isopropanol is preferably 0.1% to 1%.
The step 4）In calcining heat be 450 °C, calcination time be 30 min.
The step 5）The species of middle electrolyte is not particularly limited, specifically see embodiment.
The thickness of the sarin film is preferably 10 μm to 100 μm.
The difference of nanogold sensitization solar battery proposed by the present invention and existing similar battery is：
1. light anode is sensitized using spherical and rod-like nano gold altogether.
2. compared to single form nanogold（It is spherical or bar-shaped）The solar cell of sensitization, common sensitization solar battery
Photoresponse efficiency and energy conversion efficiency are higher.
3. by the regulation and control of the golden size of spherical and rod-like nano, realize the control that optical wavelength is responded to sensitization solar battery
System.
Brief description of the drawings
Fig. 1 represents the light anode for the different nanogold sensitization that the present invention is obtained；1 TiO2Nanometer rods, 2 TiO2Particle, 3 balls
Shape nanogold, 4 rod-like nanos gold.
The schematic diagram that Fig. 2 assembles for battery in the present invention, upper row is sectional view, and lower row is top view；5 light anodes are led
Electric glass, 6 sarin films, the TiO2 layers of 7 nanogold sensitization, the hole on 8 pairs of electrodes, 9 pairs of electrodes, 10 electrolyte.
Embodiment
The present invention further illustrates the technical characteristic of the present invention with the following example, but protection scope of the present invention is not
It is limited to the following example.
Embodiment 1
1）Prepare light anode：a）By 0.2 gTiO2Nanometer powder（21 nm, it is commercially available）It is added to water, ethanol（AR, it is commercially available）
And acetic acid（AR, it is commercially available）Mixed solvent in, wherein ethanol is 2 mL, and the volume ratio of water and ethanol is 2/3, acetic acid and ethanol
Volume ratio is that mass percent of 1/10, the TiO2 powder in mixed solvent is about 6%；b）To a）In drip in obtained mixture
Plus 0.02 g Triton X-100（AR, it is commercially available）, its mass percent in mixed solvent is about 0.6%；c）To b）In
The mixture arrived carries out 2 h of ultrasonic 10 min and stirring, until the muddy that mixture is creamy white；d）By c）In obtain milky white
Mill base material coating device is in the conductive glass surface film forming of cleaning, and the spacing control of wherein coating device and conductive glass surface is 20
μm；e）After solvent in institute's film forming volatilizees, 450 °C of 30 min of calcining in Muffle furnace are put into；f）By e）The electrode of middle gained is put into
70 °C of 40 mM TiCl4（AR, it is commercially available）In the aqueous solution, and 30 min are incubated, are then cleaned, be put into Muffle furnace with pure water
450 °C are calcined 30 min again, and the thickness of the TiO2 stratum granulosums of last gained photoanode surface is about 5 μm.
2）Prepare gold nanorods colloidal solution：a）By 0.25 mL0.01 M HAuCl4•3H2O（AR, it is commercially available）The aqueous solution adds
Enter the cetyl trimethylammonium bromide to 7.5 mL0.1 M（AR, it is commercially available）In the aqueous solution, and it is well mixed；b）By 0.6
ML0.01 M sodium borohydrides（AR, it is commercially available）The aqueous solution is added rapidly to a）In mixed solution in, and quickly mix 2 min；c）
By b）In obtained sample be put into 25 °C of water-baths, and be incubated 2 h, obtain nanogold kind solution；d）By 1.0 mL0.01 M's
HAuCl4•3H2The O aqueous solution is added in the 23.75 mL0.1 M cetyl trimethylammonium bromide aqueous solution, and is well mixed；
e）As d）In mixed solution add 0.15 mL 0.01 M silver nitrate（AR, it is commercially available）The aqueous solution, and be well mixed；f）To e）
In mixed solution in add 0.16 mL0.1 M ascorbic acid（AR, it is commercially available）The aqueous solution, and be well mixed；g）To f）In
0.05 mLc is added in mixed solution）In obtained nanogold kind solution, it is well mixed after stand overnight；h）To g）In reaction
Product is centrifuged, then is re-dispersed into 25 mL water, and golden concentration is about 0.008wt% in its dispersion liquid,
The average length and diameter of obtained gold nanorods respectively may be about 40 and 15 nm.
3）The sensitization of light anode：a）With 0.2 M NaOH（AR, it is commercially available）The aqueous solution is by 0.01 M HAuCl4•3H2O water
The pH value of solution is adjusted to 8；b）By 1）Middle preparation light anode is put into a）HAuCl after middle pH value regulation4•3H2In the O aqueous solution, and
Keep 8 h；c）Take out HAuCl4•3H2Light anode in the O aqueous solution, with being put into after pure water rinsing in Muffle furnace, 200 °C are calcined 2
H, then form spherical nanogold in TiO2 particle surfaces, and its average grain diameter is about 2.3 nm；d）By c）The spherical nanometer of middle preparation
The light anode and/or 1 of gold sensitization）The light anode not being sensitized of middle preparation is put into 1 M 3- mercaptopropionic acids（AR, it is commercially available）The aqueous solution
In, and keep 24 h；e）By d）In electrode take out, be placed in air drying after being cleaned with ethanol；f）By e）In obtained electricity
Pole is immersed in 2）In in obtained gold nanorods colloidal solution, and keep 24 h；g）By f）In obtained electrode take out, use pure water
Air drying is placed in after cleaning, this results in spherical nanogold, rod-like nano gold and both light anodes for being sensitized altogether, totally three
Kind.
4）Prepare to electrode：By 1wt% H2PtCl6•3H2O（AR, it is commercially available）Isopropanol（AR, it is commercially available）Solution drop coating is to clearly
On electro-conductive glass that is clean and punching in advance, after after isopropanol volatilization, electro-conductive glass is put into 450 °C of calcinings 30 in Muffle furnace
min。
5）The assembling of battery：a）By 3）The nanogold sensitization light anode and 4 of middle preparation）Sarin film is used electrode in middle preparation
（50 μm of thickness, it is commercially available）Bonded under 125 °C；b）By electrolyte by the aperture on electrode is injected into light anode,
In the space constituted to electrode and sarin film, wherein electrolyte is to contain 0.22 M Co (bpy)3(PF6)2（Self-control）、0.033 M
Co(bpy)3(PF6)3（Self-control）、0.1 M LiClO4（CP, it is commercially available）With 0.5 M 4-tert-butylpyridine（AR, city
Sell）Acetonitrile（AR, it is commercially available）Solution；c）With sarin film to being sealed to the aperture on electrode, the assembling of battery is completed.
I-V curve is carried out to the battery of assembling（Under the G of AM 1.5 simulated solar irradiation）Found altogether with quantum efficiency test
The energy conversion efficiency of sensitization solar battery responds optical wavelength up to 750 nm up to 1.9 %；And single spherical nanogold sensitization is too
The energy conversion efficiency of positive energy battery is 1.5 %, response optical wavelength only up to 550 nm；Single bar-shaped golden sensitization solar battery
Responding optical wavelength, sensitized cells are similar together, but energy conversion efficiency is 1.1 %.The result shows compared to single form nanometer
Gold（It is spherical or bar-shaped）The solar cell of sensitization, the photoresponse efficiency and energy conversion efficiency of common sensitization solar battery are more
It is high.
Embodiment 2
In the step 1 of embodiment 1）In, use TiO2Mean particle size is 80 nm（It is commercially available）, use surface-active
Agent is Triton X-114（AR, it is commercially available）, its concentration is 1wt%；Step 4）Middle H2PtCl6•3H2The concentration of O aqueous isopropanols is
0.5 wt%, is spin-coated on the electro-conductive glass of cleaning using 2000 rpm；Step 5）In sarin film thickness be 100 μm.To group
The battery of dress carries out the energy conversion efficiency of I-V curve and the common sensitization solar battery of quantum efficiency test discovery up to 1.8 %, rings
Optical wavelength is answered up to 750 nm；And the energy conversion efficiency of single spherical nanogold sensitization solar battery is 1.6 %, light wave is responded
Long only up to 550 nm；Sensitized cells are similar together for the response optical wavelength of single bar-shaped golden sensitization solar battery, but energy is changed
Efficiency is 1.2 %；The result shows compared to single form nanogold（It is spherical or bar-shaped）The solar cell of sensitization, altogether sensitization
The photoresponse efficiency and energy conversion efficiency of solar cell are higher.
Embodiment 3
In the step 1 of embodiment 1）Described in rubbing method be repeated 3 times in same conductive glass surface, gained TiO2 stratum granulosums
Thickness is about 13 μm；I-V curve is carried out to the battery of assembling and quantum efficiency test finds the energy of sensitization solar battery altogether
Conversion efficiency responds optical wavelength up to 750 nm up to 2.5 %；And the energy conversion effect of single spherical nanogold sensitization solar battery
Rate is 1.9 %, response optical wavelength only up to 550 nm；The response optical wavelength of single bar-shaped golden sensitization solar battery is sensitized electricity together
Pond is similar, but energy conversion efficiency is 2.0 %.The result shows compared to single form nanogold（It is spherical or bar-shaped）Sensitization
Solar cell, the photoresponse efficiency and energy conversion efficiency of sensitization solar battery are higher altogether.
Embodiment 4
In the step 1 of embodiment 1）Middle use hydro-thermal method prepares bar-shaped TiO2Light anode：a）By 30 mL water and 30 mL 36
Wt% hydrochloric acid（AR, it is commercially available）Mixed, concentration of hydrochloric acid is about 19 wt% in solution；b）A into stirring）Solution is added dropwise 0.8
ML tetra-n-butyl titanates（AR, it is commercially available）, continue after completion of dropping to stir 30 min, until resulting solution clear, gained titanium
The concentration of sour four N-butyls is about 1 wt%；c）The electro-conductive glass of cleaning is tilted to the polytetrafluoroethylene (PTFE) for being put into that volume is 100 mL
In inner liner of reaction kettle, it is conductive down, then by b）In solution pour into liner, tighten reactor, be put into 150 °C of bakings
Case reacts 20 h；d）By c）In obtained electrode be put into 450 °C of 30 min of calcining in Muffle furnace；e）By d）The electrode of middle gained
In the TiCl4 aqueous solution for being put into 70 °C of 40 mM, and 30 min are incubated, are then cleaned with pure water, be put into Muffle furnace 450 °C
30 min, gained TiO are calcined again2The average length and diameter of nanometer rods respectively may be about 7 μm and 200 nm.
I-V curve is carried out to the battery of assembling and quantum efficiency test finds that the energy of sensitization solar battery altogether changes effect
Rate responds optical wavelength up to 750 nm up to 1.4 %；And the energy conversion efficiency of single spherical nanogold sensitization solar battery is
1.0 %, response optical wavelength only up to 550 nm；The response optical wavelength of single bar-shaped golden sensitization solar battery sensitized cells class together
Seemingly, but energy conversion efficiency be 1.1 %；The result shows compared to single form nanogold（It is spherical or bar-shaped）The sun of sensitization
Energy battery, the photoresponse efficiency and energy conversion efficiency of sensitization solar battery are higher altogether.
Embodiment 5
The hydrochloric acid of 20 mL water and the wt% of 40 mL 36 is mixed in example 4, concentration of hydrochloric acid is about 25 in solution
Wt%, the quantitative change of the butyl titanate of dropwise addition is 1.6 mL, and the concentration of gained tetra-n-butyl titanate is about 2 wt%, gained after reaction
TiO2The average length and diameter of nanometer rods respectively may be about 10 μm and 500 nm.
I-V curve is carried out to the battery of assembling and quantum efficiency test finds that the energy of sensitization solar battery altogether changes effect
Rate responds optical wavelength up to 750 nm up to 1.6 %；And the energy conversion efficiency of single spherical nanogold sensitization solar battery is
1.1 %, response optical wavelength only up to 550 nm；The response optical wavelength of single bar-shaped golden sensitization solar battery sensitized cells class together
Seemingly, but energy conversion efficiency be 1.1 %.The result shows compared to single form nanogold（It is spherical or bar-shaped）The sun of sensitization
Energy battery, the photoresponse efficiency and energy conversion efficiency of sensitization solar battery are higher altogether.
Embodiment 6
In the step 2 of embodiment 4）d）In HAuCl4•3H2The concentration of the O aqueous solution is changed into 0.005 M, g）The nanometer of middle addition
It is about 0.004 wt%, obtained gold nanorods that gold, which plants solution to be changed into concentration golden in 0.1 mL, gained gold nanorods colloidal solution,
Average length and diameter respectively may be about 20 and 7 nm.
I-V curve is carried out to the battery of assembling and quantum efficiency test finds that the energy of sensitization solar battery altogether changes effect
Rate responds optical wavelength up to 710 nm up to 1.3 %；And the energy conversion efficiency of single spherical nanogold sensitization solar battery is
1.0 %, response optical wavelength only up to 550 nm；The response optical wavelength of single bar-shaped golden sensitization solar battery sensitized cells class together
Seemingly, but energy conversion efficiency be 0.8 %;The result shows compared to single form nanogold（It is spherical or bar-shaped）The sun of sensitization
Energy battery, the photoresponse efficiency and energy conversion efficiency of sensitization solar battery are higher altogether, and pass through gold nanorods size
Regulation and control realize the regulation and control that optical wavelength is responded to solar cell.
Embodiment 7
In the step 2 of embodiment 4）d）In HAuCl4•3H2The concentration of the O aqueous solution is changed into 0.05 M, by cetyl front three
The concentration of bromide aqueous ammonium is changed into 0.05 M, and golden concentration is about 0.04 in last gained gold nanorods colloidal solution
Wt%, the average length and diameter of obtained gold nanorods respectively may be about 200 and 30 nm.
I-V curve is carried out to the battery of assembling and quantum efficiency test finds that the energy of sensitization solar battery altogether changes effect
Rate responds optical wavelength up to 800 nm up to 1.1 %；And the energy conversion efficiency of single spherical nanogold sensitization solar battery is
1.0 %, response optical wavelength only up to 550 nm；The response optical wavelength of single bar-shaped golden sensitization solar battery sensitized cells class together
Seemingly, but energy conversion efficiency be 0.6 %；The result shows compared to single form nanogold（It is spherical or bar-shaped）The sun of sensitization
Energy battery, the photoresponse efficiency and energy conversion efficiency of sensitization solar battery are higher altogether, and pass through gold nanorods size
Regulation and control realize the regulation and control that optical wavelength is responded to solar cell.
Embodiment 8
In the step 3 of embodiment 4）a）In, by 0.01 M HAuCl4•3H2The pH value of the O aqueous solution is adjusted to 4.5, by c）In
Calcining heat is changed to 300 °C, and calcination time is changed to 4 h, then in TiO2Nanorod surfaces form the average grain diameter of spherical nanogold
About 4.1 nm.
I-V curve is carried out to the battery of assembling and quantum efficiency test finds that the energy of sensitization solar battery altogether changes effect
Rate responds optical wavelength up to 750 nm up to 1.4 %；And the energy conversion efficiency of single spherical nanogold sensitization solar battery is
0.9 %, response optical wavelength only up to 580 nm；The response optical wavelength of single bar-shaped golden sensitization solar battery sensitized cells class together
Seemingly, but energy conversion efficiency be 1.1 %；The result shows compared to single form nanogold（It is spherical or bar-shaped）The sun of sensitization
Energy battery, the photoresponse efficiency and energy conversion efficiency of sensitization solar battery are higher altogether, and pass through spherical nanogold size
Regulation and control realize to solar cell respond optical wavelength regulation and control.
Embodiment 9
In the step 5 of embodiment 1）The middle electrolyte used is changed to containing 0.6 M 1-butyl-3-
methylimidazolium iodide（AR, it is commercially available）、0.03 M of iodine（AR, it is commercially available）、0.1 M guanidinium
thiocyanate（AR, it is commercially available）With 0.5 M 4-tert- butylpyridine acetonitrile solution.
I-V curve is carried out to the battery of assembling and quantum efficiency test finds that the energy of sensitization solar battery altogether changes effect
Rate responds optical wavelength up to 750 nm up to 0.4 %；And the energy conversion efficiency of single spherical nanogold sensitization solar battery is
0.2 %, response optical wavelength only up to 550 nm；The response optical wavelength of single bar-shaped golden sensitization solar battery sensitized cells class together
Seemingly, but energy conversion efficiency be 0.2 %；The result shows compared to single form nanogold（It is spherical or bar-shaped）The sun of sensitization
Energy battery, the photoresponse efficiency and energy conversion efficiency of sensitization solar battery are higher altogether.
Embodiment 10
In the step 5 of embodiment 1）The middle electrolyte used is changed to containing 0.5 M LiI（AR, it is commercially available）、0.05 M of
Iodine and 0.5 M 4-tert- butylpyridine acetonitrile solution.
I-V curve is carried out to the battery of assembling and quantum efficiency test finds the energy conversion of sensitization solar battery altogether
Efficiency responds optical wavelength up to 750 nm up to 0.35 %；And the energy conversion efficiency of single spherical nanogold sensitization solar battery
For 0.2 %, response optical wavelength only up to 550 nm；The response optical wavelength of single bar-shaped golden sensitization solar battery sensitized cells together
It is similar, but energy conversion efficiency is 0.15 %；The result shows compared to single form nanogold（It is spherical or bar-shaped）Sensitization
Solar cell, the photoresponse efficiency and energy conversion efficiency of sensitization solar battery are higher altogether.
Embodiment 11
In the step 5 of embodiment 1）The middle electrolyte used is changed to containing 400 mM K4Fe(CN)6（AR, it is commercially available）、40 mM
K3Fe(CN)6（AR, it is commercially available）、100 mM KCl（AR, it is commercially available）With 50 mM Trizma-HCl buffer solutions (pH 8, commercially available)
The aqueous solution.
I-V curve is carried out to the battery of assembling and quantum efficiency test finds that the energy of sensitization solar battery altogether changes effect
Rate responds optical wavelength up to 750 nm up to 0.5 %；And the energy conversion efficiency of single spherical nanogold sensitization solar battery is
0.3 %, response optical wavelength only up to 550 nm；The response optical wavelength of single bar-shaped golden sensitization solar battery sensitized cells class together
Seemingly, but energy conversion efficiency be 0.35 %；The result shows compared to single form nanogold（It is spherical or bar-shaped）Sensitization is too
Positive energy battery, the photoresponse efficiency and energy conversion efficiency of sensitization solar battery are higher altogether.
Claims (9)
1. a kind of sensitization solar battery based on different shape nanogold, the step of its preparation method includes preparing light anode,
The assembling step of the step of the step of preparing the aqueous dispersions of gold nanorods, the sensitising step of light anode, preparation are to electrode and battery
Suddenly, it is characterised in that the sensitising step of the light anode is：First, the light anode of preparation is dipped into certain density and pH value
HAuCl4·3H2In the O aqueous solution, it is put into Muffle furnace and calcines after light anode is taken out after certain time, being cleaned with water, so that
Prepare the light anode of spherical nanogold sensitization；Then, the light anode spherical nanogold of above-mentioned preparation being sensitized is immersed in 3- mercaptos
Surface modification is carried out in the aqueous solution of base propionic acid, then the light anode after modification is immersed in the aqueous dispersions of the gold nanorods of preparation
In, take out after light anode, cleaning-drying that the spherical and golden light anode being sensitized altogether of rod-like nano is made after immersion；It is described spherical
The average grain diameter of nanogold is 1nm to 15nm；The average length and diameter of the gold nanorods be respectively 20nm to 500nm and
5nm to 50nm.
2. a kind of sensitization solar battery based on different shape nanogold as claimed in claim 1, it is characterised in that：It is described
HAuCl4·3H2The concentration of the O aqueous solution is 0.001M to 0.1M, and its pH value is 4.5 to 10, and soak time is 8h；The calcining temperature
Spend for 200 DEG C to 450 DEG C, calcination time is 2h.
3. a kind of sensitization solar battery based on different shape nanogold as claimed in claim 1, it is characterised in that：It is described
The concentration of the 3- mercaptopropionic acid aqueous solution is 0.01M to 1.0M, and golden concentration is in the aqueous dispersions of the gold nanorods
0.001wt% to 0.04wt%.
4. a kind of sensitization solar battery based on different shape nanogold as claimed in claim 1, it is characterised in that described
Prepare light anode the step of be：Certain thickness TiO is prepared on transparent conducting glass electrode first2Stratum granulosum or TiO2Nanometer
Rod layer, then calcines to obtained electrode, finally carries out TiCl4Processing.
5. a kind of sensitization solar battery based on different shape nanogold as claimed in claim 4, it is characterised in that：TiO2
The preparation method of light anode is rubbing method or hydro-thermal reaction method.
6. a kind of sensitization solar battery based on different shape nanogold as claimed in claim 5, it is characterised in that：It is described
Rubbing method is used to prepare granular TiO2Light anode：First by TiO2Nano particle is added to the mixing containing surfactant
In solvent；Then ultrasound and stirring, the muddy for making it be creamy white are carried out to solution；Then medicator is used in the conduction of cleaning
Glass surface forms uniform TiO2Pulp layer；Finally it is put into Muffle furnace and calcines after solvent volatilization is finished；Finally carry out
TiCl4Processing；The TiO2Nano particle size is 20nm to 100nm；
The mixed solvent contains water, ethanol and acetic acid, and the volume ratio of its reclaimed water and ethanol is 1/3~4/5：1, acetic acid and ethanol
Volume ratio be 1/20~1/5；1, TiO2Mass percent of the nano particle in mixed solvent is 5% to 15%；
The surfactant includes Triton X-100, Triton X-102, Triton X-114 and Triton X-165 and existed
Interior nonionic surface active agent, its mass percent in mixed solvent is 0.1% to 3%；
The TiCl4Processing is the TiCl that the concentration that the electrode after calcining is put into 70 DEG C is 40mM430 minutes in the aqueous solution, so
Cleaned afterwards with pure water, place into Muffle furnace and calcine 30min at 450 DEG C；
The rubbing method can be repeated several times in same conductive glass surface, so as to increase TiO2The thickness of nano-particle layer, the TiO2
The thickness of nano-particle layer is 5 μm to 20 μm.
7. a kind of sensitization solar battery based on different shape nanogold as claimed in claim 5, it is characterised in that：It is described
Hydro-thermal reaction method is used to prepare TiO2Nanometer rods light anode：The electro-conductive glass of cleaning is placed in the hydrochloric acid containing tetra-n-butyl titanate
In the reactor of the aqueous solution, TiO is grown in conductive glass surface by hydro-thermal reaction2Nanometer stick array, then enters to electrode
Row calcining and TiCl4Processing；
The concentration of hydrochloric acid is 10wt% to 30wt% in the aqueous hydrochloric acid solution；
Mass percent of the tetra-n-butyl titanate in aqueous hydrochloric acid solution is 0.1wt% to 5wt%；
The hydrothermal reaction condition is that closed reactor is put into 150 DEG C of baking oven to react 20h；
The calcine technology is to calcine 30min in 450 DEG C of Muffle furnace；
The TiCl4Processing refers to the TiCl that the concentration that the electrode after calcining is put into 70 DEG C is 40mM430 minutes in the aqueous solution, so
Cleaned afterwards with pure water, place into Muffle furnace and calcine 30min at 450 DEG C；
The TiO2The length and diameter of nanometer rods are respectively 3 μm to 12 μm and 0.2 μm to 1 μm；Thickness is the length of rod.
8. a kind of sensitization solar battery based on different shape nanogold as claimed in claim 1, it is characterised in that described
The step of aqueous dispersions for preparing gold nanorods is：First, with HAuCl4·3H2O is as golden presoma, with cetyl three
Methyl bromide ammonium prepares nanogold kind using sodium borohydride as reducing agent as surfactant；Then, with HAuCl4·3H2O
As the presoma of gold, using cetyl trimethylammonium bromide as surfactant, using ascorbic acid as reducing agent, and profit
Gold nanorods are grown with the nanogold kind and silver nitrate of above-mentioned preparation, finally unnecessary surface-active are removed using the method for centrifugation
Agent, and gold nanorods are dispersed in water standby；
The preparation of the nanogold kind is first by HAuCl4·3H2The O aqueous solution and the cetyl trimethylammonium bromide aqueous solution enter
Row mixing, is then rapidly added sodium borohydride aqueous solution thereto, and is stirred vigorously, and above-mentioned solution finally is put into 25 DEG C
2h is aged in water-bath；
The HAuCl4·3H2The concentration of the O aqueous solution is 0.01M；
The concentration of the cetyl trimethylammonium bromide aqueous solution is 0.1M；
The concentration of the sodium borohydride aqueous solution is 0.01M；
HAuCl4·3H2The volume ratio of the O aqueous solution, the cetyl trimethylammonium bromide aqueous solution and sodium borohydride aqueous solution is：
0.25：7.5：0.6；
The preparation of the gold nanorods is by HAuCl4·3H2The O aqueous solution, silver nitrate aqueous solution and aqueous ascorbic acid are successively
It is added in the cetyl trimethylammonium bromide aqueous solution and is well mixed, then adds the nanogold kind solution prepared,
Finally stand overnight；
The HAuCl4·3H2The concentration of the O aqueous solution is 0.002M to 0.1M；
The concentration of the silver nitrate aqueous solution is 0.01M；
The concentration of the aqueous ascorbic acid is 0.1M；
The concentration of the cetyl trimethylammonium bromide aqueous solution is 0.01M to 0.2M；
The mass percent of the nanogold kind GOLD FROM PLATING SOLUTION is 5.9 × 10-3%；
HAuCl4·3H2The O aqueous solution, silver nitrate aqueous solution, aqueous ascorbic acid, the cetyl trimethylammonium bromide aqueous solution
Volume ratio with nanogold kind solution is：1：0.15：0.16：23.75：0.02-0.2.
9. a kind of sensitization solar battery based on different shape nanogold as claimed in claim 1, it is characterised in that described
Prepare to electrode the step of be：By H2PtCl6·3H2O aqueous isopropanol is coated on the transparent conducting glass punched in advance
On, calcined after being put into after solvent volatilization in Muffle furnace；
The painting method to electrode is drop coating or spin coating；
The H2PtCl6·3H2The concentration of O aqueous isopropanols is 0.1% to 1%；
The calcining heat is 450 DEG C, and calcination time is 30min；
The number of assembling steps of the battery be by the nanogold of preparation is sensitized light anode and prepare use electrode certain thickness sand
Woods film is bonded under conditions of heating, then by electrolyte by being injected into light anode, to electrode to the aperture on electrode
In the space constituted with sarin film, finally the assembling of battery is completed to being sealed to the aperture on electrode with sarin film；It is described
The thickness of sarin film is 10 μm to 100 μm.
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