CN105895377B - A kind of all-weather solar battery that can be generated electricity at night and its preparation method and application - Google Patents
A kind of all-weather solar battery that can be generated electricity at night and its preparation method and application Download PDFInfo
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- CN105895377B CN105895377B CN201610407919.1A CN201610407919A CN105895377B CN 105895377 B CN105895377 B CN 105895377B CN 201610407919 A CN201610407919 A CN 201610407919A CN 105895377 B CN105895377 B CN 105895377B
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- afterglow material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Abstract
The present invention provides a kind of all-weather solar batteries that can be generated electricity at night and its preparation method and application, the present invention is specifically to be combined dye-sensitized solar cells with long-afterglow material, it is formed in the all-weather solar battery that day and night can generate electricity, the present invention makes full use of long-afterglow material to absorb sunlight on daytime, night excite fluorescence the characteristics of and fluorescent lifetime it is long, the high advantage of luminous intensity, conventional solar cell is overcome can not generate electricity under the conditions of dark situation the shortcomings that, assign the performance that solar cell generates electricity in dark situation, really realize the round-the-clock power generation of solar cell；Moreover, solar cell preparation process of the present invention is simple, generating dutation is long, stability is high, of low cost, there is important practical value and economic value.
Description
Technical field
The invention belongs to technical field of solar batteries, and in particular to a kind of all-weather solar electricity that can be generated electricity at night
Pond and its preparation method and application.
Background technology
Dye-sensitized solar cells is one kind by porous silica nanocrystalline Ti light anode, sensitizing dyestuff, I-/I3 -Electrolysis
Matter and the electrochemical appliance that solar energy can be changed into electric energy to electrode composition, good with stability, preparation process is simple, clearly
The advantages that clean pollution-free.But it can only be used under conditions of daytime is sunny, this so that its application range and generated energy are big
It is big to reduce, therefore a kind of round-the-clock dye-sensitized solar cells that can be generated electricity at night is developed with highly important meaning
Justice.
Invention content
The purpose of the present invention is being directed to the shortcomings that conventional dyes sensitization solar battery can not generate electricity in dark situation, provide
A kind of all-weather solar battery that can be generated electricity at night and its preparation method and application.The present invention is by long-afterglow material spin coating
In on mesoporous titanium dioxide film, it is assembled into dye-sensitized solar cells jointly.One aspect of the present invention can so that dyestuff is quick
Change solar cell at night utmostly using fluorescence, improve the generated energy of battery；On the other hand, long-afterglow material is at low cost
Honest and clean, technical maturity can make dye-sensitized solar cells generate electricity in dark surrounds.
For achieving the above object, the present invention is achieved by the following scheme：
A kind of preparation method of all-weather solar battery that can be generated electricity at night, the preparation method include following step
Suddenly：
(1), colloidal tio 2 is prepared, colloidal tio 2 is uniformly applied on FTO glass matrix and obtains titanium dioxide
Film；
(2), long-afterglow material is uniformly dispersed in ethanol, prepares long-afterglow material slurry；
(3), it by the titanium deoxid film in the uniform spin coating in step (1) of long-afterglow material slurry, through calcining, obtains
Obtain long-afterglow material/mesoporous titanium dioxide film；
(4), the long-afterglow material/mesoporous titanium dioxide film is immersed in dye solution and adsorbed, is prepared
Dye sensitization long-afterglow material/mesoporous TiO 2 light anode；
(5), electrode and dye sensitization long-afterglow material/mesoporous TiO 2 light anode will be combined, and in centre
Injection contains I-/I3 -The liquid electrolyte of oxidation-reduction pair is assembled into the all-weather solar electricity that can be generated electricity at night
Pond.
Further：The film thickness of control titanium deoxid film is 5~15 microns in the step (1).
Further：A concentration of 0.125~0.3g/mL of long-afterglow material slurry described in the step (2).
Further：The long-afterglow material grain size used in the step (2) is 1~5 micron.
Further：Spin coating rotating speed is 2500~3000 revs/min in the step (3), and spin-coating time is 10~20 seconds.
Further：Long-afterglow material described in the step (4)/mesoporous titanium dioxide film immersion 0.2~
It is adsorbed in the N719 dye solutions of 0.5mmol/L.
Further：In the step (5) is platinum, platinum alloy, compound, conducting polymer or carbon to electrode to electrode
In one kind；The liquid electrolyte is by 0.01~0.06mol/L iodine, 0.08~0.12mol/L lithium iodides, 0.4~0.8mol/
L tetrabutylammonium iodides and the acetonitrile solution of 0.4~0.6mol/L 4- tert .-butylpyridines composition.
The present invention also provides utilize the all-weather solar battery that can be generated electricity made from the preparation method at night.
Further：The all-weather solar battery is in intensity of illumination 100mW/cm2Under open-circuit voltage for 700~
750V, short-circuit current density are 15~18mA/cm2, fill factor be 65~75%, photoelectric conversion efficiency is 7~10%；
Open-circuit voltage of the all-weather solar battery under night is 200~400mV, short-circuit current density 0.8
~1.5mA/cm2, fill factor be 60~70%, photoelectric conversion efficiency is 20~50%.
The present invention also provides the all-weather solar battery in battery component, power station and craftwork is used to prepare
Application.
Compared with prior art, it advantages of the present invention and has the technical effect that：The present invention makes full use of long-afterglow material white
It absorbs sunlight and the characteristic in night excitation fluorescence, by itself and the compound preparation light anode of mesoporous titanium dioxide film, and
Round-the-clock dye-sensitized solar cells is assembled into, light source is provided at night for dye-sensitized solar cells, makes it at night
Also it can generate electricity, it is made really to realize the round-the-clock power generation of dye-sensitized solar cells, so as to which conventional dyes be overcome to be sensitized the sun
The problem of cannot generating electricity at battery night；In addition, long-afterglow material is cheap, mature preparation process, while have illumination with
Ornamental value, therefore be conducive to the commercial applications of the present invention.
Dye-sensitized solar cells preparation process prepared by the present invention is simple, generating dutation is long, stability is high, at low cost
It is honest and clean.The present invention can be not only used for generating electricity under illumination, can have important practical value with broader applications in dark situation etc.
And economic value.
Description of the drawings
Fig. 1 be the present invention prepared by round-the-clock dye-sensitized solar cells schematic diagram, wherein a：Round-the-clock dyestuff is quick
The structure for changing solar cell and the luminous schematic diagram on daytime；b：The round-the-clock dye-sensitized solar cells of green fluorescence
Structure and the luminous schematic diagram at night；c：The structure of the round-the-clock dye-sensitized solar cells of purple fluorescence and
The luminous schematic diagram at night；d：The structure of the round-the-clock dye-sensitized solar cells of blue-fluorescence and show in the luminous of night
It is intended to；e：The structure of the round-the-clock dye-sensitized solar cells of blue-green fluorescent and the luminous schematic diagram at night；f：In vain
The structure of the round-the-clock dye-sensitized solar cells of color fluorescence and the luminous schematic diagram at night；g：The whole day of red fluorescence
The structure for waiting dye-sensitized solar cells and the luminous schematic diagram at night.
Fig. 2 is the round-the-clock dye-sensitized solar cells prepared by conventional dyes sensitization solar battery and the present invention
J-V curves under simulated solar illumination and under dark situation.
Fig. 3 is the round-the-clock dye-sensitized solar cells prepared by conventional dyes sensitization solar battery and the present invention
J-V curves under dark situation.
Fig. 4 is the round-the-clock dye-sensitized solar cells prepared by conventional dyes sensitization solar battery and the present invention
(a) impedance spectrum and (b) baud compose.
Fig. 5 is the absorption spectrogram of mesoporous titanium dioxide film used in the present invention.
Fig. 6 is the transmitting spectrogram of long-afterglow material used in the present invention.
Fig. 7 is that ornamental value of the round-the-clock dye-sensitized solar cells used in the present invention at night is shown, wherein Fig. 7 a, figure
7b, Fig. 7 c, Fig. 7 d, Fig. 7 e, Fig. 7 f represent the light that solar cell night sends out and are followed successively by green, purple, blue, bluish-green respectively
Color, white, red.
Specific embodiment
Technical scheme of the present invention is described in further detail With reference to embodiment.
Embodiment 1
First, the preparation method of all-weather solar battery of the present invention that can be generated electricity at night specifically includes following step
Suddenly：
1st, colloidal tio 2 is prepared using sol-gel self-combustion synthesis, colloidal tio 2 is applied on FTO glass matrix and is made
Titanium deoxid film, control film thickness are 10 microns；
2nd, long-afterglow material is uniformly dispersed in ethanol, compound concentration is the long-afterglow material slurry of 0.25g/mL；
3rd, using spin-coating method, the long-afterglow material slurry in step 2 is uniformly spin-coated on titanium dioxide made from step 1
In titanium film (spin coating rotating speed is 3000 revs/min, and spin-coating time is 20 seconds), calcined 30 minutes through 450 DEG C, obtain long afterglow material
Material/mesoporous titanium dioxide film；
4th, the long-afterglow material for preparing step 3/mesoporous titanium dioxide film immerses the N719 dyes of 0.25mmol/L
It is adsorbed 24 hours in material solution, dye sensitization long-afterglow material/mesoporous TiO 2 light anode is prepared；
5th, the dye sensitization long-afterglow material/mesoporous TiO 2 light anode for preparing step 4 with to electrode combination,
And it is assembled into all-weather solar battery in centre injection liquid electrolyte.It is described to electrode for platinum, platinum alloy, compound, lead
Electric polymer or carbon are to one kind in electrode；The liquid electrolyte includes 0.01~0.06mol/L iodine, 0.08~0.12mol/
The acetonitrile solution of L lithium iodides, 0.4~0.8mol/L tetrabutylammonium iodides and 0.4~0.6mol/L 4- tert .-butylpyridines.
According to the above method, the all-weather solar battery that can be generated electricity at night of acquisition is in simulated solar illumination
(intensity of illumination：100mW/cm2) under open-circuit voltage be 700~750mV, short-circuit current density is 15~18mA/cm2, filling because
Son is 65~75%, photoelectric conversion efficiency is 7~10%.Open-circuit voltage under night is 200~400mV, short circuit current is close
It spends for 0.01~1mA/cm2, fill factor be 60~70%, photoelectric conversion efficiency is 20~50%.
Fig. 1 be the all-weather solar battery of the present invention that can be generated electricity at night (a) daytime and (b) green fluorescence,
When (c) purple fluorescence, (d) blue-fluorescence, (e) blue-green fluorescent, (f) white fluorescent and (g) red fluorescence night generate electricity
Schematic diagram.It can be seen from the figure that the assembling mode and dependency structure of all-weather solar battery.The all-weather solar
Battery includes four parts：The light anode of dye sensitization, long-afterglow material, to electrode and I-/I3 -Electrolyte.Its principle is：In vain
During its illumination abundance, the sun for dye-sensitized solar cells provides light source so that dye-sensitized solar cells generates electricity, meanwhile,
Long-afterglow material can also absorb light.Night, long-afterglow material can send out fluorescence, be provided for dye-sensitized solar cells at night
Light source makes it that can also generate electricity at night.
All-weather solar battery is assembled according to structure shown in Fig. 1, using electrochemical workstation CHI660E to the electricity of battery
Chemical property is tested, and test result is as shown in Figure 2, Figure 3 and Figure 4.
Fig. 2 is the simulation of the all-weather solar battery prepared by traditional dye-sensitized solar cells and the present invention
Under solar irradiation and the J-V curves at night.As can be seen from Figure 2 using long-afterglow material/mesoporous TiO 2 complex light sun
The dye-sensitized solar cells of pole can generate electricity at night, but since long afterglow light intensity is weaker, current density is smaller.
In addition, in one layer of long-afterglow material of titanium dioxide surface spin coating, it can stop the electronics and I of light anode excitation-/I3 -Electrolyte weight
It is new compound, so as to which open-circuit voltage increases.Since long-afterglow material granularity is larger, the electronics of light anode excitation is needed across more than length
Brightness material and titanium deoxid film get to FTO glass and are passed to external circuit, extend electron-transport time, certain electronics hairs
Raw quenching, so as to reduce the short-circuit current density of battery.By calculating, the efficiency of traditional dye-sensitized solar cells can
To reach 8.294%, the efficiency of round-the-clock dye-sensitized solar cells is followed successively by：The efficiency of green light is 7.731%, purple light
Efficiency is 7.359%, and the efficiency of blue light is 7.230%, and the efficiency of blue green light is 7.112%, and the efficiency of white light is 6.694%,
The efficiency of feux rouges is 6.418%.All-weather solar battery of the present invention reaches dye-sensitized solar cells commercialization should
Standard (efficiency is more than 5%).
Dark situations of the Fig. 3 for the all-weather solar battery prepared by conventional dyes sensitization solar battery and the present invention
Under J-V curves.From Fig. 3 can with it is further seen that, the all-weather solar battery can generate electricity under dark situation.
Its current density has significant difference with traditional dye-sensitized solar cells dark current density.Wherein short-circuit current density is opened
Road voltage and fill factor are green light successively, purple light, blue light, blue green light, white light, feux rouges.Related data is shown in Table 1.This knot
Fruit proves that the present invention can be achieved on the all-weather solar battery to generate electricity at night.
The traditional dye-sensitized solar cells of table 1 and all-weather solar cell photovoltaic parameter
Fig. 4 is (a) of the all-weather solar battery prepared by traditional dye-sensitized solar cells and the present invention
Impedance spectrum and (b) baud are composed.Find out from Fig. 4 a, the impedance diagram of the all-weather solar battery prepared by the present invention is all by three
A semicircle composition, respectively by I-/I3 -Electrolyte/to electrode interface transmission resistance, I-/I3 -Electrolyte/light anode interface transmission electricity
Resistance and diffusion resistance composition.Contact resistance is impedance curve and the intersection point of X-axis.Find out from Fig. 4 a, in mesoporous TiO 2
Long-afterglow material is introduced on film, it is not notable to the Resistance Influence of dye-sensitized solar cells.According to the π f of formula τ=1/2,
Wherein τ represent electron lifetime, f represent baud spectrogram in low frequency peak peak position, obtain electronics by electrolyte by long-afterglow material with
And titanium deoxid film is transferred to service life of FTO glass and is slightly reduced.Related data is shown in Table 2.
2 conventional dyes sensitization solar battery of table and all-weather solar battery impedance and electron lifetime
Fig. 5 is the absorption spectrogram of mesoporous titanium dioxide film used in the present invention.From figure 5 it can be seen that mesoporous two
Thin film of titanium oxide can absorb wavelength as there are two stronger absorptions at 350nm~600nm, 500~540nm and 390~440nm
Peak.
The transmitting spectrogram of long-afterglow material that Fig. 6 is applied for the present invention.From being seen from Fig. 6, long-afterglow material hair
Penetrating peak is：Green light is 450~600nm, and peak position is 500~520nm；Purple light is 380~520nm, and peak position is 430~450nm；It is blue
Light is 420~560nm, and peak position is 460~480nm；Blue green light is 420~560nm, and peak position is 460~490nm；White light is 410
~580nm, peak position are 460~480nm；Feux rouges is 585~640nm, and peak position is 590~595nm, 613~618nm and 623
~628nm.
It can be obtained from Fig. 5 and Fig. 6, used long-afterglow material launch wavelength can in mesoporous titanium dioxide film
In the wave-length coverage of absorption.Wherein green light is corresponding with the launch wavelength of purple light and the most strong absworption peak of titanium deoxid film, therefore,
The all-weather solar battery for sending out the long-afterglow material assembling of green light and purple light obtains larger short circuit current under dark situation
Density and open-circuit voltage.
Fig. 7 is that ornamental value of the all-weather solar battery used in the present invention at night is shown.Large area uses long afterglow material
While the dye-sensitized solar cells prepared during material has ornamental value, illumination can be regarded and used.
The above embodiments are merely illustrative of the technical solutions of the present invention rather than is limited；Although with reference to aforementioned reality
Example is applied the present invention is described in detail, it for those of ordinary skill in the art, still can be to aforementioned implementation
Technical solution recorded in example modifies or carries out equivalent replacement to which part technical characteristic；And these are changed or replace
It changes, the spirit and scope for claimed technical solution of the invention that it does not separate the essence of the corresponding technical solution.
Claims (2)
1. a kind of all-weather solar battery that can be generated electricity at night, it is characterised in that the solar cell passes through following preparation
Method is made：
(1), colloidal tio 2 is prepared, colloidal tio 2 is uniformly applied on FTO glass matrix and obtains titanium deoxid film,
The film thickness for controlling titanium deoxid film is 5 ~ 15 microns；
(2), long-afterglow material is uniformly dispersed in ethanol, prepares long-afterglow material slurry；The long-afterglow material slurry
A concentration of 0.125 ~ 0.3 g/mL；Long-afterglow material grain size is 1 ~ 5 micron；
(3), it by the titanium deoxid film in the uniform spin coating in step (1) of long-afterglow material slurry, through calcining, is grown
Afterglowing material/mesoporous titanium dioxide film；Spin coating rotating speed is 2500 ~ 3000 revs/min, and spin-coating time is 10 ~ 20 seconds；
(4), the long-afterglow material/mesoporous titanium dioxide film is immersed in the N719 dye solutions of 0.2~0.5 mmol/L
It is adsorbed, dye sensitization long-afterglow material/mesoporous TiO 2 light anode is prepared；
(5), electrode and dye sensitization long-afterglow material/mesoporous TiO 2 light anode will be combined, and will be injected in centre
Liquid electrolyte containing I-/I3- oxidation-reduction pairs is assembled into the all-weather solar battery that can be generated electricity at night,
It is described to electrode for platinum, platinum alloy, compound, conducting polymer or carbon to one kind in electrode；The liquid electrolyte by
0.01 ~ 0.06 mol/L iodine, 0.08 ~ 0.12 mol/L lithium iodides, 0.4 ~ 0.8 mol/L tetrabutylammonium iodides and 0.4 ~ 0.6
The acetonitrile solution composition of mol/L 4- tert .-butylpyridines；
The all-weather solar battery is in intensity of illumination 100mW/cm2Under open-circuit voltage it is close for 700 ~ 750mV, short circuit current
It spends for 15 ~ 18mA/cm2, fill factor be that 65 ~ 75%, photoelectric conversion efficiency is 7 ~ 10%；
Open-circuit voltage of the all-weather solar battery under night is 200 ~ 400mV, short-circuit current density be 0.8 ~
1.5mA/cm2, fill factor be that 60 ~ 70%, photoelectric conversion efficiency is 20 ~ 50%.
2. application of the all-weather solar battery described in claim 1 in battery component, power station and craftwork is used to prepare.
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| CN1949544A (en) * | 2006-10-30 | 2007-04-18 | 华中科技大学 | Visible light response solar energy battery |
| CN101436468A (en) * | 2008-12-09 | 2009-05-20 | 彩虹集团公司 | Light-emitting board for prolonging dye sensitization solar battery operating time |
| CN103400700A (en) * | 2013-08-08 | 2013-11-20 | 中国海洋大学 | Dye-sensitized solar cell based on binary low-platinum alloy counter electrode and preparation method and applications thereof |
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- 2016-06-07 CN CN201610407919.1A patent/CN105895377B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1949544A (en) * | 2006-10-30 | 2007-04-18 | 华中科技大学 | Visible light response solar energy battery |
| CN101436468A (en) * | 2008-12-09 | 2009-05-20 | 彩虹集团公司 | Light-emitting board for prolonging dye sensitization solar battery operating time |
| CN103400700A (en) * | 2013-08-08 | 2013-11-20 | 中国海洋大学 | Dye-sensitized solar cell based on binary low-platinum alloy counter electrode and preparation method and applications thereof |
Non-Patent Citations (1)
| Title |
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| "Multistep electrochemical deposition of hierarchical platinum alloy counter electrodes for dye-sensitized solar cells";Junjun Zhang等;《Journal of Power Sources》;20151114;第303卷;第243-249页 * |
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