CN106395892A - Method for preparing sea urchin shaped titanium dioxide hollow microsphere - Google Patents
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Abstract
The invention discloses a method for preparing sea urchin shaped titanium dioxide hollow microsphere. The method comprises the steps that 1, dispersing ordinary titanium dioxide hollow microspheres in a 10 mol / L solution, then transferring to a polytetrafluoroethylene reactor; 2, sealing the polytetrafluoroethylene reactor then placing in an oven, heating to 120 to 150 DEG C, and thermal insulation reacting for 1-3 hours, after completion of the reaction, cooling naturally to room temperature, filtering, and resulting in filter residue A, rinsing the filter residue A with distilled water to neutral, and drying naturally; 3, dispersing the residue A dried naturally in diluted hydrochloric acid, rinsing, filtrating, and resulting in filter residue B, rinsing the residue B with distilled water to neutral, and drying naturally; 4, placing the naturally dried residue B in a muffle furnace, heating to 400 DEG C at the heating rate of 1 DEG C / min, after 1 hour thermal insulation, cooling naturally to room temperature. The sea urchin shaped titanium dioxide hollow microsphere prepared by the method has large specific surface area and strong light absorption performance, and exhibits excellent photoelectric conversion performance in the area of dye sensitization solar cell.
Description
Technical field
The present invention relates to the preparing technical field of solaode new material is and in particular to a kind of Hemicentrotus seu Strongylocentrotuss shape titanium dioxide is empty
The preparation method of heart microsphere.
Background technology
In recent years, DSSC (DSSC) is due to cheap, and is easily prepared into soft device, and is considered as
The most potential novel solar battery replacing traditional silicon solar cell.Titanium dioxide is due to having good biochemistry
Inertia, anti-light corrosion and resistance to chemical corrosion, are ideal dye-sensitized photoelectric converting materials.
Document report, titanium dioxide pattern, pore passage structure, degree of crystallinity are impact DSSC photoelectric conversions
The key factor of efficiency.Up to the present, nano-particle, nanotube, the titanium dioxide of nanometer sheet, nano wire and Nano microsphere pattern
Titanium, is used as dye-sensitized solar cells photo cathode material.It is believed that bigger serface and excellent absorbing properties,
Be conducive to improving the electricity conversion of DSSC.But specific surface area and absorbing properties are often contradiction
's.For example, the titania nanoparticles of a diameter of 20nm have higher specific surface area, are conducive to dye molecule (sensitizer)
Absorption；But because titanium dioxide granule is smaller in size than visible wavelength, so the titanium deoxid film prepared is often
Transparent, thus it is unfavorable for the absorption of light.Comparatively, the titanium dioxide nanoplate that the length of side is more than 50 nanometers, can effectively inhale
Receive sunlight, but its specific surface area is again too little, be unfavorable for the absorption of sensitizer, therefore prepared nanometer sheet membrane electrode,
Electricity conversion undesirable (Nanoscale, 2010,2,2144 2149).
In order to solve the above problems, recent material supply section scholars use the titanium dioxide powder of two kinds of different sizes and pattern
(nano-particle and nanometer sheet) carries out gradient combination, the DSSC of preparation composite concentration gradient
(Nanoscale,2014,6,2390–2396).The method has taken into account nano-particle, and (bigger serface strengthens to sensitizing dyestuff
Absorption) and nanometer sheet (enhanced light scattering and absorbent properties) advantage, improve the photoelectric conversion of DSSC
Efficiency.But, the gradient combination of two kinds of different-shape titanium dioxide, need the slurry of the serial different-shape titanium dioxide ratio of preparation
Material, leads to the preparation procedure of electrode film extremely complex.
Content of the invention
For solving the problems, such as above-mentioned prior art, the invention provides a kind of Hemicentrotus seu Strongylocentrotuss shape titanic oxide hollow microballoon
Preparation method, with the titanic oxide hollow microballoon of the method preparation, not only has big specific surface area, simultaneously its absorbing properties
Also it been significantly enhanced, the Hemicentrotus seu Strongylocentrotuss shape hollow-core construction that this may be unique with it is relevant.
Realizing the technical scheme that above-mentioned purpose of the present invention used is：
A kind of preparation method of Hemicentrotus seu Strongylocentrotuss shape titanic oxide hollow microballoon, comprises the steps：
1) by ordinary titanium dioxide tiny balloon (synthetic method reference literature：Applied Catalysis B:
Environmental, 2014,147,789-795) add in the alkali liquor of 10mol/L, titanic oxide hollow microballoon and alkali mole
Than for 1:80, after dispersed with stirring is uniform, it is transferred in ptfe autoclave；
2) it is placed in after ptfe autoclave being sealed in baking oven, be heated to 120-150 DEG C, insulation reaction 1-3 hour,
After the completion of reaction, ptfe autoclave is naturally cooled to room temperature, the mixed system of gained after reaction is filtered, obtains filtering residue
A, filtering residue A is washed with distilled water to neutrality, naturally dries；
3) by step 2) in the filtering residue A that naturally dries dispersed with stirring in dilute hydrochloric acid uniformly, filter, obtain filtering residue B, by filtering residue
B is washed with distilled water to neutrality, naturally dries；
4) by step 3) in the filtering residue B that naturally dries be placed in muffle furnace, the method using temperature programming is heated up, and rises
Warm speed is 1 DEG C/min, is incubated 1 hour, naturally cools to room temperature, obtain Hemicentrotus seu Strongylocentrotuss shape titanium dioxide hollow micro- after being warming up to 400 DEG C
Ball.
Further, step 1) in, described alkali is NaOH or KOH.
Compared with prior art, advantages of the present invention and having the beneficial effects that：
1) the method is simple to operation, agents useful for same and equipment is common is easy to get, cheap, thus preparation cost is low.
2) the Hemicentrotus seu Strongylocentrotuss shape titanic oxide hollow microballoon of the method preparation, not only has big specific surface area, and its light is inhaled
Receive performance to significantly increase.Prepare thin film electrode of dye-sensitized solar cell with it, show excellent opto-electronic conversion performance.With
Compared with bi-component (nano-particle and nanometer sheet) Concentraton gradient membrane electrode, it is that slurry applies film preparation electricity with Hemicentrotus seu Strongylocentrotuss shape tiny balloon
The technique of very thin films is simpler, thus has broad application prospects.
Brief description
Fig. 1 is the X-ray diffractogram of sample S1-S6.
Fig. 2 is stereoscan photograph (a and b (enlarged drawing)) and the transmission electron microscope photo (c and d (enlarged drawing)) of sample S1.
Fig. 3 is stereoscan photograph (a and b (enlarged drawing)) and the transmission electron microscope photo (c and d (enlarged drawing)) of sample S2.
Fig. 4 is stereoscan photograph (a and b (enlarged drawing)) and the transmission electron microscope photo (c and d (enlarged drawing)) of sample S3.
Fig. 5 is stereoscan photograph (a and b (enlarged drawing)) and the transmission electron microscope photo (c and d (enlarged drawing)) of sample S4.
Fig. 6 is stereoscan photograph (a and b (enlarged drawing)) and the transmission electron microscope photo (c and d (enlarged drawing)) of sample S5.
Fig. 7 is stereoscan photograph (a and b (enlarged drawing)) and the transmission electron microscope photo (c and d (enlarged drawing)) of sample S6.
Fig. 8 is the UV-vis DRS spectrogram of sample S1-S6 powder.Fig. 9 is dye sensitization photo-anode film S1-S6
UV-vis DRS spectrogram.
Figure 10 is the I-V curve figure of battery S1-S6.
(nitrogen adsorption desorption is used to survey specific surface area the nitrogen adsorption desorption isotherm figure for sample S1-S6 for the Figure 11
).
Figure 12 is that the nitrogen adsorption of sample S1-S6 is desorbed the corresponding graph of pore diameter distribution (hole of graph of pore diameter distribution explanation sample
Distribution situation).(from pore distribution curve as can be seen that the mesoporous of ordinary titanium dioxide microsphere concentrates on macropore path portion, and alkali is warm
Process the Hemicentrotus seu Strongylocentrotuss shape titanium dioxide microballoon sphere obtaining, it assumes existing diplopore distribution, occurs in that aperture simultaneously.The appearance of aperture, be
Due to caused by the burr structure of Hemicentrotus seu Strongylocentrotuss.The generation of burr, substantially increases specific surface area and the avtive spot of catalyst,
Be conducive to the raising of efficiency of dye-sensitized solar battery).
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.
The test of embodiment 1-5 and comparative example 1 is done as described below：
1) XRD test is carried out to sample using German Bruker-D8 type X-ray diffractometer (Cu K α, λ=0.154nm)
(step-length of this X-ray diffractometer is 0.02 °/s, and running voltage and operating current are respectively 15kV and 30mA).
2) transmission electron microscope (TEM, Tecnai G20 type) of FEI Co. of U.S. production and Japanese Hitachi are adopted
The scanning electron microscope (FESEM, model S4800) that company produces carrys out pattern (transmission electron microscope during test of observing samples
Running voltage is 200Kv, and the accelerating potential of scanning electron microscope is 10Kv).
Comparative example 1
Raw material titanic oxide hollow microballoon used in embodiment 1-5 is made by oneself for inventor, and its preparation method is (with reference to literary composition
Offer Applied Catalysis B:Environmental 2014,147,789-795).Concrete preparation process is as follows：
1) under magnetic stirring, respectively 1.19 grams of ammonium titanium fluorides (analysis is pure) and 2.42 grams of carbamide (analysis is pure) are added to
In polytetrafluoroethylene beaker equipped with 65 milliliters of distilled water, stir to after be completely dissolved, add 15 milliliters of hydrogen peroxide
(40wt%, analysis is pure), immediately the brownish red mixed solution of gained being transferred to volume is 100 milliliters of band polytetrafluoroethyllining lining
Stainless steel cauldron in.
2) it is placed in baking oven after will be airtight for stainless steel cauldron, be heated to 200 DEG C, insulation reaction 10 hours, reaction completes
Afterwards, treat that stainless steel cauldron is cooled to room temperature (20-30 DEG C), the mixed system of gained after reaction is filtered, by the white of gained
Filtering residue is filtered with filter membrane (0.45 micron of filter sizes), filter cake is washed with distilled water to neutral (pH=7), finally naturally dries in the air
Dry, obtain final product titanic oxide hollow microballoon, be labeled as sample S1.
The titanic oxide hollow microballoon (sample S1) of above-mentioned preparation is carried out X-ray diffraction test, its X-ray diffractogram is such as
Shown in Fig. 1 (a), from Fig. 1 (a) as can be seen that the crystal formation of sample S1 is Detitanium-ore-type.
The titanic oxide hollow microballoon (sample S1) of above-mentioned preparation is scanned Electronic Speculum and transmissioning electric mirror test, its scanning
Electronic Speculum is with transmission electron microscope picture as shown in Fig. 2 figure it is seen that S1 sample is hollow-core construction.
Embodiment 1
1) 0.5g titanic oxide hollow microballoon (its synthetic method is specifically shown in comparative example 1) is added 50ml 10mol/L's
In NaOH solution, after dispersed with stirring 10min, it is transferred in ptfe autoclave (band outer lining rustless steel)；
2) it is placed in after ptfe autoclave being sealed in baking oven, be heated to 120 DEG C, insulation reaction 1 hour, react
Cheng Hou, ptfe autoclave is naturally cooled to room temperature (20-30 DEG C), the mixed system of gained after reaction is filtered, obtains
Filtering residue A, filtering residue A is washed with distilled water to neutral (pH=7), naturally dries；
3) by step 2) in the filtering residue A that naturally dries add in the dilute hydrochloric acid of 600ml 0.1mol/L, magnetic agitation 12 is little
Shi Hou, filters, obtains filtering residue B, filtering residue B is washed with distilled water to neutral (pH=7), naturally dries；
4) by step 3) in the filtering residue B that naturally dries be placed in muffle furnace, the method using temperature programming is heated up, and rises
Warm speed is 1 DEG C/min, is incubated 1 hour, naturally cools to room temperature, obtain Hemicentrotus seu Strongylocentrotuss shape titanium dioxide hollow micro- after being warming up to 400 DEG C
Ball, is labeled as sample S2.
The Hemicentrotus seu Strongylocentrotuss shape titanic oxide hollow microballoon (sample S2) of above-mentioned preparation is carried out X-ray diffraction test, its X-ray is spread out
Penetrate shown in figure such as Fig. 1 (b), from Fig. 1 (b) as can be seen that sample S2 crystal formation be still Detitanium-ore-type.
The Hemicentrotus seu Strongylocentrotuss shape titanic oxide hollow microballoon (sample S2) of above-mentioned preparation is scanned Electronic Speculum and transmissioning electric mirror test,
Its scanning electron microscope is with transmission electron microscope picture as shown in figure 3, from figure 3, it can be seen that alkali is warm, calcining and other processes do not make sample S2 hollow
Structure collapses, and played fold on surface, Hemicentrotus seu Strongylocentrotuss shape initially forms.
Embodiment 2
1) 0.5g titanic oxide hollow microballoon (its synthetic method is specifically shown in comparative example 1) is added 50ml 10mol/L's
In NaOH solution, after dispersed with stirring 10min, it is transferred in ptfe autoclave (band outer lining rustless steel)；
2) it is placed in after ptfe autoclave being sealed in baking oven, be heated to 120 DEG C, insulation reaction 2 hours, react
Cheng Hou, ptfe autoclave is naturally cooled to room temperature (20-30 DEG C), the mixed system of gained after reaction is filtered, obtains
Filtering residue A, filtering residue A is washed with distilled water to neutral (pH=7), naturally dries；
3) by step 2) in the filtering residue A that naturally dries add in the hydrochloric acid of 600ml 0.1mol/L, magnetic agitation 12 hours
Afterwards, filter, obtain filtering residue B, filtering residue B is washed with distilled water to neutral (pH=7), naturally dries；
4) by step 3) in the filtering residue B that naturally dries be placed in muffle furnace, the method using temperature programming is heated up, and rises
Warm speed is 1 DEG C/min, is incubated 1 hour, naturally cools to room temperature, obtain Hemicentrotus seu Strongylocentrotuss shape titanium dioxide hollow micro- after being warming up to 400 DEG C
Ball, is labeled as sample S3.
The Hemicentrotus seu Strongylocentrotuss shape titanic oxide hollow microballoon (sample S3) of above-mentioned preparation is carried out X-ray diffraction test, its X-ray is spread out
Penetrate shown in figure such as Fig. 1 (c), from Fig. 1 (c) as can be seen that sample S3 crystal formation be still Detitanium-ore-type.
The Hemicentrotus seu Strongylocentrotuss shape titanic oxide hollow microballoon (sample S3) of above-mentioned preparation is scanned Electronic Speculum and transmissioning electric mirror test,
Its scanning electron microscope is with transmission electron microscope picture as shown in figure 4, from fig. 4, it can be seen that alkali is warm, calcining and other processes do not make sample S3 hollow
Structure collapses, and increase burr on surface, in Hemicentrotus seu Strongylocentrotuss shape.
Embodiment 3
1) 0.5g titanic oxide hollow microballoon (its synthetic method is specifically shown in comparative example 1) is added 50ml 10mol/L's
In NaOH solution, after dispersed with stirring 10min, it is transferred in ptfe autoclave (band outer lining rustless steel)；
2) it is placed in after ptfe autoclave being sealed in baking oven, be heated to 120 DEG C, insulation reaction 3 hours, react
Cheng Hou, ptfe autoclave is naturally cooled to room temperature (20-30 DEG C), the mixed system of gained after reaction is filtered, obtains
Filtering residue A, filtering residue A is washed with distilled water to neutral (pH=7), naturally dries；
3) by step 2) in the filtering residue A that naturally dries add in the dilute hydrochloric acid of 600ml 0.1mol/L, magnetic agitation 12 is little
Shi Hou, filters, obtains filtering residue B, filtering residue B is washed with distilled water to neutral (pH=7), naturally dries；
4) by step 3) in the filtering residue B that naturally dries be placed in muffle furnace, the method using temperature programming is heated up, and rises
Warm speed is 1 DEG C/min, is incubated 1 hour, naturally cools to room temperature, obtain Hemicentrotus seu Strongylocentrotuss shape titanium dioxide hollow micro- after being warming up to 400 DEG C
Ball, is labeled as sample S4.
The Hemicentrotus seu Strongylocentrotuss shape titanic oxide hollow microballoon (sample S4) of above-mentioned preparation is carried out X-ray diffraction test, its X-ray is spread out
Penetrate shown in figure such as Fig. 1 (d), from Fig. 1 (d) as can be seen that sample S4 crystal formation be still Detitanium-ore-type.
The Hemicentrotus seu Strongylocentrotuss shape titanic oxide hollow microballoon (sample S4) of above-mentioned preparation is scanned Electronic Speculum and transmissioning electric mirror test,
Its scanning electron microscope is with transmission electron microscope picture as shown in figure 5, from fig. 5, it can be seen that alkali is warm, calcining and other processes do not make sample S4 hollow
Structure collapses, and increase burr on surface, in Hemicentrotus seu Strongylocentrotuss shape.
Embodiment 4
1) 0.5g titanic oxide hollow microballoon (its synthetic method is specifically shown in comparative example 1) is added 50ml 10mol/L's
In KOH solution, after dispersed with stirring 10min, it is transferred in ptfe autoclave (band outer lining rustless steel)；
2) it is placed in after ptfe autoclave being sealed in baking oven, be heated to 120 DEG C, insulation reaction 3 hours, react
Cheng Hou, ptfe autoclave is naturally cooled to room temperature (20-30 DEG C), the mixed system of gained after reaction is filtered, obtains
Filtering residue A, filtering residue A is washed with distilled water to neutral (pH=7), naturally dries；
3) by step 2) in the filtering residue A that naturally dries add in the dilute hydrochloric acid of 600ml 0.1mol/L, magnetic agitation 12 is little
Shi Hou, filters, obtains filtering residue B, filtering residue B is washed with distilled water to neutrality, naturally dries；
4) by step 3) in the filtering residue B that naturally dries be placed in muffle furnace, the method using temperature programming is heated up, and rises
Warm speed is 1 DEG C/min, is incubated 1 hour, naturally cools to room temperature, obtain Hemicentrotus seu Strongylocentrotuss shape titanium dioxide hollow micro- after being warming up to 400 DEG C
Ball, is labeled as sample S5.
The Hemicentrotus seu Strongylocentrotuss shape titanic oxide hollow microballoon (sample S5) of above-mentioned preparation is carried out X-ray diffraction test, its X-ray is spread out
Penetrate shown in figure such as Fig. 1 (e), from Fig. 1 (e) as can be seen that sample S5 crystal formation be still Detitanium-ore-type.
The Hemicentrotus seu Strongylocentrotuss shape titanic oxide hollow microballoon (sample S5) of above-mentioned preparation is scanned Electronic Speculum and transmissioning electric mirror test,
Its scanning electron microscope is with transmission electron microscope picture as shown in fig. 6, from fig. 6, it can be seen that alkali is warm, calcining and other processes do not make sample S5 hollow
Structure collapses, and increase burr on surface, in Hemicentrotus seu Strongylocentrotuss shape.
Embodiment 5
1) 0.5g titanic oxide hollow microballoon (its synthetic method is specifically shown in comparative example 1) is added 50ml 10mol/L's
In NaOH solution, after dispersed with stirring 10min, it is transferred in ptfe autoclave (band outer lining rustless steel)；
2) it is placed in after ptfe autoclave being sealed in baking oven, be heated to 150 DEG C, insulation reaction 1 hour, react
Cheng Hou, ptfe autoclave is naturally cooled to room temperature (20-30 DEG C), the mixed system of gained after reaction is filtered, obtains
Filtering residue A, filtering residue A is washed with distilled water to neutral (pH=7), naturally dries；
3) by step 2) in the filtering residue A that naturally dries add in the dilute hydrochloric acid of 600ml 0.1mol/L, magnetic agitation 12 is little
Shi Hou, filters, obtains filtering residue B, filtering residue B is washed with distilled water to neutrality, naturally dries；
4) by step 3) in the filtering residue B that naturally dries be placed in muffle furnace, the method using temperature programming is heated up, and rises
Warm speed is 1 DEG C/min, is incubated 1 hour, naturally cools to room temperature, obtain Hemicentrotus seu Strongylocentrotuss shape titanium dioxide hollow micro- after being warming up to 400 DEG C
Ball, is labeled as sample S6.
The Hemicentrotus seu Strongylocentrotuss shape titanic oxide hollow microballoon (sample S6) of above-mentioned preparation is carried out X-ray diffraction test, its X-ray is spread out
Penetrate shown in figure such as Fig. 1 (f), from Fig. 1 (f) as can be seen that sample S6 crystal formation be still Detitanium-ore-type.
The Hemicentrotus seu Strongylocentrotuss shape titanic oxide hollow microballoon (sample S6) of above-mentioned preparation is scanned Electronic Speculum and transmissioning electric mirror test,
Its scanning electron microscope is with transmission electron microscope picture as shown in fig. 7, from figure 7 it can be seen that alkali is warm, calcining and other processes do not make sample S4 hollow
Structure collapses, and overgrow with burr on surface, in Hemicentrotus seu Strongylocentrotuss shape.
UV-vis DRS spectrum analyses are carried out to sample S1-S6 (powder), its UV-vis DRS spectrogram
As shown in figure 8, as shown in Figure 8, with respect to sample S1, sample S2-S6 ultraviolet region light absorbs strengthen, and illustrate what alkali process obtained
Hemicentrotus seu Strongylocentrotuss shape titanic oxide hollow microballoon, its absorbing properties strengthens, and is conducive to improving electricity conversion.
Prepared by comparative example 1 with sample S1, the physical property of the sample S2-S6 of embodiment 2-5 preparation is tested, test knot
Fruit is as shown in Figure 11, Figure 12 and table 1：
The physical property of table 1 sample S1-S6
Test one, measurement are prepared by the use of the Hemicentrotus seu Strongylocentrotuss shape titanic oxide hollow microballoon of method of the present invention preparation as light anode
DSSC electricity conversion
Experimental technique：
1st, the preparation of light anode titanium deoxid film：According to document Nanoscale, 2010,2,2144-2149 technique
1) weigh 1.5g sample S1 in viscous alms bowl, in viscous alms bowl, then add 6.5 milliliters of dehydrated alcohol, 2.0 milliliters of distillations
Water, 0.5 milliliter of acetylacetone,2,4-pentanedione and 1.0 milliliters of TritonX (Tirton X-100) are after the material mix homogeneously in viscous alms bowl, manual
Mill 15 minutes, obtain titania slurry；
2) by above-mentioned titania slurry with doctor blade method even application on FTO electro-conductive glass, surface covered be 1.0cm2,
By coated FTO conductive glass electrode, calcine 30 minutes in 450 DEG C, obtain titanium dioxide thin film photo-anode S1 and (control dioxy
Change 10 microns of the thickness of titanium film).
Sample S2-S6 is used to make titanium dioxide thin film photo-anode S2-S6 according to the method described above.
2nd, prepare the assembling of DSSC；
1) titanium dioxide thin film photo-anode S1 is soaked in the ethanol solution of 0.3mM ruthenium pyridine (N719) 12 hours
Afterwards, take out to be put in 80 DEG C of baking ovens and be dried 2 hours, obtain dye sensitization photo-anode film S1.
2) according to step 1) method preparation dye sensitization photo-anode film S2-S6.To dye sensitization photo-anode film S2-
S6 carries out UV-vis DRS spectrum analyses, and its UV-vis DRS spectrogram is as shown in figure 9,528nm is sensitizer
The characteristic absorption peak of N719, peak illustrates that more by force absorbing dye is more, is more conducive to the raising of electricity conversion, as shown in Figure 9,
The characteristic absorption peak of the sensitizer N719 of dye sensitization photo-anode film S2-S6 will much be better than dye sensitization photo-anode film
S1, illustrates that the absorbing properties of dye sensitization photo-anode film S2-S6 significantly increase.
3) dye sensitization photo-anode film S1-S6 is assembled into DSSC, respectively battery S1, battery
S2, battery S3, battery S4, battery S5 and battery S6.The method being assembled into battery is as follows：Using sandwich structure, upper and lower electrode
Be respectively the conductive glass electrode (to electrode) of titanium dioxide membrane electrode provided (light anode) and platinum plating, between upper and lower electrode away from
From about 50 microns, with capillary tube injection method up, fill between bottom electrode electrolyte (electrolyte consists of 0.3M LiI,
0.05M I2, the anhydrous acetonitrile of 0.6M 1- propyl group -3- Methylimidazole. and 0.5M tert .-butylpyridine).
3rd, the test of DSSC electrical property
It is respectively completed the battery S1 of above-mentioned assembling, battery S2, battery S3, battery S4, electricity in CHI660C electrochemical workstation
The characteristic test of current-voltage (I-V) of pond S5 and battery S6.Light source adopts Newport 91160 solar simulator,
Light intensity is 100mW cm-2(1 standard sun light intensity).During test, the light-receiving area of dye cell is 4 × 4mm2.Dye sensitization
The electricity conversion (η) of solaode is calculated with formula 1：
η (%)=Voc×ISC×FF×100/Pin(formula 1)
In formula 1, VocFor open-circuit photovoltage, ISCFor short-circuit photocurrent, FF is compactedness, PinFor incident photon energy.
Result of the test is as shown in table 2 below and Figure 10：
The performance parameter of table 2. DSSC S1-S7
As can be seen from Table 1 and Table 2, with NaOH as alkali source, the response time is to be within 2 hours titanic oxide hollow microballoon alkali
Heat treatment optimum condition, with this understanding, the specific surface area (154m of sample S32g-1) with respect to sample S1 (21m2g-1) increased
6 times.As can be seen here, the Hemicentrotus seu Strongylocentrotuss shape titanic oxide hollow microballoon that alkali process obtain, its unique structure leads to absorbing properties to increase
By force (Fig. 8), big specific surface area also enhances the absorption (Fig. 9) of sensitizer, this two big factor, is all conducive to improving dye sensitization
Solar cell photoelectric transformation efficiency.
Claims (2)
1. a kind of preparation method of Hemicentrotus seu Strongylocentrotuss shape titanic oxide hollow microballoon is it is characterised in that comprise the steps：
1) titanic oxide hollow microballoon is added in the alkali liquor of 10mol/L, titanic oxide hollow microballoon is 1 with the mol ratio of alkali:
80, after dispersed with stirring is uniform, it is transferred in ptfe autoclave；
2) it is placed in after ptfe autoclave being sealed in baking oven, be heated to 120-150 DEG C, insulation reaction 1-3 hour, reaction
After the completion of, ptfe autoclave is naturally cooled to room temperature, the mixed system of gained after reaction is filtered, obtains filtering residue A, will
Filtering residue A is washed with distilled water to neutrality, naturally dries；
3) by step 2) in the filtering residue A that naturally dries stirring reaction 12 hours in the hydrochloric acid of 0.1mol/L, filter, obtain filtering residue B,
Filtering residue B is washed with distilled water to neutrality, naturally dries；
4) by step 3) in the filtering residue B that naturally dries be placed in muffle furnace, the method using temperature programming is heated up, and heat up speed
Rate is 1 DEG C/min, is incubated 1 hour, naturally cools to room temperature, obtain Hemicentrotus seu Strongylocentrotuss shape titanic oxide hollow microballoon after being warming up to 400 DEG C.
2. Hemicentrotus seu Strongylocentrotuss shape titanic oxide hollow microballoon according to claim 1 preparation method it is characterised in that：Step 1)
In, described alkali is NaOH or KOH.
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| CN108686592A (en) * | 2018-05-21 | 2018-10-23 | 陕西科技大学 | A kind of preparation method of sea urchin shape bivalve layer hollow microsphere |
| CN109292816A (en) * | 2018-09-20 | 2019-02-01 | 济南大学 | The preparation method of paper base sea urchin shape titanium dioxide |
| CN109437293A (en) * | 2018-11-30 | 2019-03-08 | 中南民族大学 | A kind of nonmetallic codope thorn shape inlays TiO2Hollow structure and its preparation method and application |
| CN110038560A (en) * | 2019-04-28 | 2019-07-23 | 河南大学 | A kind of sea urchin shape hollow platinum/titanium dioxide nano material, preparation method and application of oxygen-containing vacancy |
| CN114471193A (en) * | 2022-03-07 | 2022-05-13 | 四川轻化工大学 | Filtering membrane with ultraviolet-resistant self-cleaning function and application thereof |
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| 蔡晶华: ""二氧化钛空心微球微结构调控及其增强的光催化活性"", 《中南民族大学硕士学位论文》 * |
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| CN108686592A (en) * | 2018-05-21 | 2018-10-23 | 陕西科技大学 | A kind of preparation method of sea urchin shape bivalve layer hollow microsphere |
| CN108686592B (en) * | 2018-05-21 | 2020-11-13 | 陕西科技大学 | Preparation method of sea urchin-shaped double-shell hollow microspheres |
| CN109292816A (en) * | 2018-09-20 | 2019-02-01 | 济南大学 | The preparation method of paper base sea urchin shape titanium dioxide |
| CN109437293A (en) * | 2018-11-30 | 2019-03-08 | 中南民族大学 | A kind of nonmetallic codope thorn shape inlays TiO2Hollow structure and its preparation method and application |
| CN109437293B (en) * | 2018-11-30 | 2021-01-29 | 中南民族大学 | Nonmetal co-doped thorn-shaped embedded TiO2Hollow structure and preparation method and application thereof |
| CN110038560A (en) * | 2019-04-28 | 2019-07-23 | 河南大学 | A kind of sea urchin shape hollow platinum/titanium dioxide nano material, preparation method and application of oxygen-containing vacancy |
| CN114471193A (en) * | 2022-03-07 | 2022-05-13 | 四川轻化工大学 | Filtering membrane with ultraviolet-resistant self-cleaning function and application thereof |
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