CN106206033B - A kind of solar battery - Google Patents
A kind of solar battery Download PDFInfo
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- CN106206033B CN106206033B CN201610510596.9A CN201610510596A CN106206033B CN 106206033 B CN106206033 B CN 106206033B CN 201610510596 A CN201610510596 A CN 201610510596A CN 106206033 B CN106206033 B CN 106206033B
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- tungsten oxide
- fto
- oxide nano
- dye
- solution
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- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 98
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 98
- 239000011521 glass Substances 0.000 claims abstract description 86
- 239000000758 substrate Substances 0.000 claims abstract description 78
- 239000003792 electrolyte Substances 0.000 claims abstract description 46
- 239000011258 core-shell material Substances 0.000 claims abstract description 38
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims abstract description 15
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 57
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 49
- 239000000975 dye Substances 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 28
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 23
- 229910052721 tungsten Inorganic materials 0.000 claims description 22
- 239000010937 tungsten Substances 0.000 claims description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 239000000919 ceramic Substances 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- 230000003647 oxidation Effects 0.000 claims description 17
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- 239000002105 nanoparticle Substances 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 15
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 14
- 238000013019 agitation Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 238000004851 dishwashing Methods 0.000 claims description 14
- 229960004756 ethanol Drugs 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 229910052740 iodine Inorganic materials 0.000 claims description 14
- 239000011630 iodine Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 239000002086 nanomaterial Substances 0.000 claims description 10
- 239000002070 nanowire Substances 0.000 claims description 10
- 230000008859 change Effects 0.000 claims description 9
- 239000008151 electrolyte solution Substances 0.000 claims description 9
- 230000004807 localization Effects 0.000 claims description 9
- 238000004544 sputter deposition Methods 0.000 claims description 8
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- 239000000908 ammonium hydroxide Substances 0.000 claims description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 7
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 7
- 238000000137 annealing Methods 0.000 claims description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 7
- 239000000428 dust Substances 0.000 claims description 7
- 238000005516 engineering process Methods 0.000 claims description 7
- 239000004744 fabric Substances 0.000 claims description 7
- 239000012467 final product Substances 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 238000002347 injection Methods 0.000 claims description 7
- 239000007924 injection Substances 0.000 claims description 7
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- -1 removes greasy dirt Substances 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 7
- 239000001509 sodium citrate Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 7
- 238000002207 thermal evaporation Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000010408 film Substances 0.000 description 35
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 7
- 206010070834 Sensitisation Diseases 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 238000002242 deionisation method Methods 0.000 description 6
- 230000005611 electricity Effects 0.000 description 6
- 238000011010 flushing procedure Methods 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 230000008313 sensitization Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000001235 sensitizing effect Effects 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
Abstract
This application involves a kind of solar battery, the solar battery is based on dye-sensitized solar cells, and the dye-sensitized solar cells are constituted by light anode, to electrode and electrolyte；Tungsten oxide nano, the glass microballoon coated on tungsten oxide nano bottom that the structure of the light anode is FTO substrate from outside to inside, is grown on FTO substrate surface；The tungsten oxide nano is core-shell structure, and core is tungsten oxide nano, and shell is titanium oxide；Described is FTO substrate, reflective layer, Pt Catalytic Layer from outside to inside to electrode；Antifreezing agent normal propyl alcohol is added in the electrolyte.
Description
Technical field
This application involves area of solar cell more particularly to a kind of solar batteries.
Background technique
The energy is all movable bases of production of human society, with the development of modern economy, demand of the mankind to the energy
Just become to increasingly sharpen.The reserves of traditional energy are limited, and content is becoming more and more exhausted, and since traditional energy exists
Using a large amount of toxic and harmful gas, solid etc. can be generated in the process, have become the arch-criminal of the environmental pollution got worse.
Based on this, develop the research emphasis that new and renewable energy is 21st century.Wherein, solar energy resources depend on the sun
Light is a kind of inexhaustible clean energy resource.In recent years, solar photovoltaic industry is developed rapidly, and exploitation is cheap, efficient
Solar battery have become the research hotspot of current academic activities, business activity.
Dye-sensitized solar cells (DSSC) is a kind of electrooptical device of nanostructure, generally by five part groups
At respectively electrically conducting transparent substrate, Nanometer Semiconductor Films, dye sensitizing agent, electrolyte and to electrode.Dye sensitizing agent is realized
The function of light absorption, after dye molecule absorbs sunlight, electronics occurs transition and injects in the conduction band of Nanometer Semiconductor Films,
Then by flowing out through electrode, operating current is generated, hole stays in the dye molecule of oxidation state by the redox in electrolyte
To reduction, ground state is returned in dye molecule transition, to absorb photon again；The electrolyte of oxidation state is then diffused to electrode, due to
Catalyst film is coated with to electrode surface, reduction reaction occurs for electrolyte under the action of catalyst, so far completes optical electro-chemistry
The circulation of reaction.
Dye-sensitized solar cells are cheap since manufacturing process is simple, high-efficient, have very wide market and answer
Use prospect.However, can generate corrosiveness since electrolyte solution is generally in acidity to Nanometer Semiconductor Films, influence dyestuff
It is sensitized the job stability of solar cell；In addition, using TiO2 particle as nanometer half in general dye-sensitized solar cells
Conductor thin film easily causes the compound of electronics, to drop since the big specific surface area of TiO2 nanometer particle film and defect exist
Low photoelectric conversion efficiency.
Summary of the invention
To overcome the problems in correlation technique, the application provides a kind of solar battery.
The application is achieved through the following technical solutions:
A kind of solar battery, the solar battery are based on dye-sensitized solar cells, the dye sensitization sun electricity
Pond is constituted by light anode, to electrode and electrolyte；The structure of the light anode is FTO substrate from outside to inside, is grown on FTO base
The tungsten oxide nano of bottom surface, the glass microballoon coated on tungsten oxide nano bottom；The tungsten oxide nano is nucleocapsid
Structure, core are tungsten oxide nano, and shell is titanium oxide；It is described that electrode is catalyzed for FTO substrate from outside to inside, reflective layer, Pt
Layer；Antifreezing agent normal propyl alcohol is added in the electrolyte.
Preferably, the preparation step of the dye-sensitized solar cells is as follows:
Step 1 makes FTO substrate:
A) it cleans FTO substrate: selecting FTO electro-conductive glass as the substrate of light anode, firstly, cutting FTO electro-conductive glass, is used
The conductive one side of ultra-clean cloth wiping FTO for speckling with dish washing liquid, removes the impurity such as greasy dirt, dust existing for surface, then uses deionization
Water repeated flushing for several times, until dish washing liquid is cleaned up, is put it into ozone clean machine, ozone treatment 10min, then according to
It is cleaned by ultrasonic 30min respectively according to the sequence of acetone, ethyl alcohol, deionized water, is dried up with nitrogen gun stand-by；
B) it grows tungsten oxide nano: the metal of one layer of 150nm thickness is deposited on the surface FTO using magnetron sputtering technology
Tungsten film grows source as tungsten oxide nano, while realizing that the localization of tungsten film is grown using ceramic template, in magnetron sputtering process
Ceramic template is attached to the surface FTO, wherein the pore diameter of ceramic template is 2 μm, and spacing is 50 μm, magnetron sputtering electric current
For 2A；Tungsten oxide nano growth uses thermal oxidation process, and the FTO electro-conductive glass for being coated with tungsten film is put into thermal evaporation furnace,
Under the protection of inert gas, 400 DEG C of heat preservation 5h are taken out after natural cooling；
C) it prepares core-shell structure tungsten oxide nano: weighing the ethanol solution of 100ml, be added 1ml's
C16H36O4Ti is stirred evenly under 70 DEG C of water-baths, has the FTO electro-conductive glass of tungsten oxide nano to be put into solution growth,
11s is stood, is then quickly removed, which repeats five times, can guarantee that nanowire surface adequately superscribes
The sample of taking-up is then had core-shell structure tungsten oxide nano by shell structure to obtain the final product after 400 DEG C of annealing 1h, natural cooling
FTO substrate；
Step 2 adsorbs glass microballoon:
The glass microballoon (Glass Bead Diameter is 5~10 μm) for taking 20g to buy is cleaned with deionized water, dry, is added to
It is filtered by vacuum after magnetic agitation 20min in the hydrofluoric acid solution of 20mol/l, it is dry after being cleaned with deionized water to neutrality, it removes
Ionized water 100ml sequentially adds 2.5g sodium citrate, 2.2g ammonium sulfate and 5g nano silver particles, and ammonium hydroxide is then added and adjusts pH
Value is 6, dry glass microballoon is added in above-mentioned solution, at 60 DEG C, magnetic agitation 2h is cooled to room temperature after reaction；It will
FTO substrate obtained in step 1 with core-shell structure tungsten oxide nano immerses in above-mentioned solution, stands at 80 DEG C of water-bath
5h can form glass microballoon combination core-shell structure tungsten oxide nano-material in FTO substrate surface.
Step 3 is prepared to electrode:
The FTO electro-conductive glass for choosing size identical as light anode, then in one layer of Ag of its surface magnetic control sputtering, as reflective
Then Pt catalyst layer is deposited with a thickness of 300nm in layer, Ag again, Pt catalyst layer thickness is 50nm.
Step 4 assembles dye-sensitized solar cells:
Electrolyte apply traditional three anion electrolyte of iodine/iodine: weigh the acetonitrile solution of 100ml first, thereto plus
Entering the lithium iodide of 0.1M, 0.1M iodine, the tetrabutylammonium iodide of 0.6M 4- tert .-butylpyridine and 0.6M is protected from light ultrasonic 5min,
It dissolves it sufficiently, then weighs the nano TiO 2 nanoparticle of 8g, under 70 degrees Celsius of water-bath, TiO2 nanoparticle is added
In electrolyte solution, it is eventually adding 5ml antifreezing agent normal propyl alcohol, ultrasonic 30min is mixed them thoroughly uniformly；
Dye solution: weighing N719 powder 50mg, and N719 is added to absolute ethanol by dehydrated alcohol 30ml, sufficiently dissolves,
It is protected from light stirring 12h.It takes the dye solution of above-mentioned preparation to be put into brown glass ware, FTO substrate is then entered into the brown glass
It in ware, is protected from light and is sensitized 3h at 60 DEG C, take out, be then packaged together to electrode and the light anode, encapsulating material is using heat-sealing
Film encapsulates aperture, it is quick to form improvement type dye of the invention for connecting wire by electrolyte from the aperture injection to electrode one end
Change solar battery.
The technical solution that embodiments herein provides can include the following benefits:
1. using the tungsten oxide nano-material of core-shell structure in solar battery light anode of the invention, wherein oxidation
Tungsten belongs to semiconductor material with wide forbidden band, has excellent electric conductivity, can guarantee that electronics quickly transmits；In addition, tungsten oxide is received
Rice noodles use core-shell structure, can effectively hinder the compound of electronics, while the structure can effectively reduce acid dyes pair
The corrosion of tungsten oxide nano improves the stability of dye cell；In dye-sensitized solar cells light anode, in core-shell structure oxygen
The gap for changing tungsten nanowires is adsorbed with soot-particles, forms microballon-nanowire structure, which can effectively increase the sun
The scattering of light so that dyestuff greatly improves the absorptivity of sunlight, and then improves the photoelectric conversion efficiency of solar battery.
2. in the electrolyte of solar cell of the present invention, TiO2 nanoparticle joined, the partial size of the nanoparticle is 30~
70nm can play scattering process to sunlight, so that dyestuff improves the absorption efficiency of sunlight, to improve the battery
Photoelectric conversion efficiency.
3. tungsten oxide nano has certain density in dye-sensitized solar cell anode, and using simple
Template realizes localization growth, easy to operate, low in cost, has certain market prospects.
The additional aspect of the application and advantage will be set forth in part in the description, and will partially become from the following description
It obtains obviously, or recognized by the practice of the application.It should be understood that above general description and following detailed description are only
Be it is exemplary and explanatory, the application can not be limited.
Detailed description of the invention
The drawings herein are incorporated into the specification and forms part of this specification, and shows and meets implementation of the invention
Example, and be used to explain the principle of the present invention together with specification.
Fig. 1 is solar cell production flow diagram of the invention.
Specific embodiment
Example embodiments are described in detail here, and the example is illustrated in the accompanying drawings.Following description is related to
When attached drawing, unless otherwise indicated, the same numbers in different drawings indicate the same or similar elements.Following exemplary embodiment
Described in embodiment do not represent all embodiments consistented with the present invention.On the contrary, they be only with it is such as appended
The example of device and method being described in detail in claims, some aspects of the invention are consistent.
Following disclosure provides many different embodiments or example is used to realize the different structure of the application.For letter
Change disclosure herein, hereinafter the component of specific examples and setting are described.Certainly, they are merely examples, and
Purpose does not lie in limitation the application.In addition, the application can in different examples repeat reference numerals and/or letter.It is this heavy
It is that for purposes of simplicity and clarity, itself is more than the relationship discussed between various embodiments and/or setting again.This
Outside, this application provides various specific techniques and material example, but those of ordinary skill in the art may be aware that
The use of the applicability and/or other materials of other techniques.In addition, fisrt feature described below is in Second Eigenvalue "upper"
Structure may include embodiment that the first and second features are formed as directly contacting, also may include that other feature is formed in
Embodiment between first and second features, such first and second feature may not be direct contact.
In the description of the present application, it should be noted that unless otherwise specified and limited, term " installation ", " connected ",
" connection " shall be understood in a broad sense, for example, it may be mechanical connection or electrical connection, the connection being also possible to inside two elements can
, can also indirectly connected through an intermediary, for the ordinary skill in the art to be to be connected directly, it can basis
Concrete condition understands the concrete meaning of above-mentioned term.
The energy is all movable bases of production of human society, with the development of modern economy, demand of the mankind to the energy
Just become to increasingly sharpen.The reserves of traditional energy are limited, and content is becoming more and more exhausted, and since traditional energy exists
Using a large amount of toxic and harmful gas, solid etc. can be generated in the process, have become the arch-criminal of the environmental pollution got worse.
Based on this, develop the research emphasis that new and renewable energy is 21st century.Wherein, solar energy resources depend on the sun
Light is a kind of inexhaustible clean energy resource.In recent years, solar photovoltaic industry is developed rapidly, and exploitation is cheap, efficient
Solar battery have become the research hotspot of current academic activities, business activity.
Dye-sensitized solar cells (DSSC) is a kind of electrooptical device of nanostructure, generally by five part groups
At respectively electrically conducting transparent substrate, Nanometer Semiconductor Films, dye sensitizing agent, electrolyte and to electrode.Dye sensitizing agent is realized
The function of light absorption, after dye molecule absorbs sunlight, electronics occurs transition and injects in the conduction band of Nanometer Semiconductor Films,
Then by flowing out through electrode, operating current is generated, hole stays in the dye molecule of oxidation state by the redox in electrolyte
To reduction, ground state is returned in dye molecule transition, to absorb photon again；The electrolyte of oxidation state is then diffused to electrode, due to
Catalyst film is coated with to electrode surface, reduction reaction occurs for electrolyte under the action of catalyst, so far completes optical electro-chemistry
The circulation of reaction.
Dye-sensitized solar cells are cheap since manufacturing process is simple, high-efficient, have very wide market and answer
Use prospect.However, can generate corrosiveness since electrolyte solution is generally in acidity to Nanometer Semiconductor Films, influence dyestuff
It is sensitized the job stability of solar cell；In addition, using TiO2 particle as nanometer half in general dye-sensitized solar cells
Conductor thin film easily causes the compound of electronics, to drop since the big specific surface area of TiO2 nanometer particle film and defect exist
Low photoelectric conversion efficiency.
The present invention is based on the light anode structures of dye-sensitized solar cells, first in the transparent electrode surface magnetic of light anode
The tungsten oxide film of control one layer of localization of sputtering is set by nanowire growth, and after nano wire is made into core-shell structure on its surface
It is equipped with glass microballoon structure, produces unexpected beneficial effect.
The present invention will be further explained with reference to the examples below.
Embodiment 1:
Embodiments herein is related to a kind of solar battery, and the solar battery is based on dye-sensitized solar cells,
The dye-sensitized solar cells are constituted by light anode, to electrode and electrolyte；The structure of the light anode is from outside to inside
FTO substrate, the tungsten oxide nano for being grown on FTO substrate surface, the glass microballoon coated on tungsten oxide nano bottom；It is described
Tungsten oxide nano is core-shell structure, and core is tungsten oxide nano, and shell is titanium oxide；Described is FTO from outside to inside to electrode
Substrate, reflective layer, Pt Catalytic Layer；Antifreezing agent normal propyl alcohol is added in the electrolyte.
Preferably, such as Fig. 1, the preparation step of the dye-sensitized solar cells is as follows:
Step 1 makes FTO substrate:
A) it cleans FTO substrate: selecting FTO electro-conductive glass as the substrate of light anode, firstly, cutting FTO electro-conductive glass, is used
The conductive one side of ultra-clean cloth wiping FTO for speckling with dish washing liquid, removes the impurity such as greasy dirt, dust existing for surface, then uses deionization
Water repeated flushing for several times, until dish washing liquid is cleaned up, is put it into ozone clean machine, ozone treatment 10min, then according to
It is cleaned by ultrasonic 30min respectively according to the sequence of acetone, ethyl alcohol, deionized water, is dried up with nitrogen gun stand-by；
B) it grows tungsten oxide nano: the metal of one layer of 150nm thickness is deposited on the surface FTO using magnetron sputtering technology
Tungsten film grows source as tungsten oxide nano, while realizing that the localization of tungsten film is grown using ceramic template, in magnetron sputtering process
Ceramic template is attached to the surface FTO, wherein the pore diameter of ceramic template is 2 μm, and spacing is 50 μm, magnetron sputtering electric current
For 2A；Tungsten oxide nano growth uses thermal oxidation process, and the FTO electro-conductive glass for being coated with tungsten film is put into thermal evaporation furnace,
Under the protection of inert gas, 400 DEG C of heat preservation 5h are taken out after natural cooling；
C) it prepares core-shell structure tungsten oxide nano: weighing the ethanol solution of 100ml, be added 1ml's
C16H36O4Ti is stirred evenly under 70 DEG C of water-baths, has the FTO electro-conductive glass of tungsten oxide nano to be put into solution growth,
11s is stood, is then quickly removed, which repeats five times, can guarantee that nanowire surface adequately superscribes
The sample of taking-up is then had core-shell structure tungsten oxide nano by shell structure to obtain the final product after 400 DEG C of annealing 1h, natural cooling
FTO substrate；
Step 2 adsorbs glass microballoon:
The glass microballoon (Glass Bead Diameter is 5~10 μm) for taking 20g to buy is cleaned with deionized water, dry, is added to
It is filtered by vacuum after magnetic agitation 20min in the hydrofluoric acid solution of 20mol/l, it is dry after being cleaned with deionized water to neutrality, it removes
Ionized water 100ml sequentially adds 2.5g sodium citrate, 2.2g ammonium sulfate and 5g nano silver particles, and ammonium hydroxide is then added and adjusts pH
Value is 6, dry glass microballoon is added in above-mentioned solution, at 60 DEG C, magnetic agitation 2h is cooled to room temperature after reaction；It will
FTO substrate obtained in step 1 with core-shell structure tungsten oxide nano immerses in above-mentioned solution, stands at 80 DEG C of water-bath
5h can form glass microballoon combination core-shell structure tungsten oxide nano-material in FTO substrate surface.
Step 3 is prepared to electrode:
The FTO electro-conductive glass for choosing size identical as light anode, then in one layer of Ag of its surface magnetic control sputtering, as reflective
Then Pt catalyst layer is deposited with a thickness of 300nm in layer, Ag again, Pt catalyst layer thickness is 50nm.
Step 4 assembles dye-sensitized solar cells:
Electrolyte apply traditional three anion electrolyte of iodine/iodine: weigh the acetonitrile solution of 100ml first, thereto plus
Entering the lithium iodide of 0.1M, 0.1M iodine, the tetrabutylammonium iodide of 0.6M 4- tert .-butylpyridine and 0.6M is protected from light ultrasonic 5min,
It dissolves it sufficiently, then weighs the nano TiO 2 nanoparticle of 8g, under 70 degrees Celsius of water-bath, TiO2 nanoparticle is added
In electrolyte solution, it is eventually adding 5ml antifreezing agent normal propyl alcohol, ultrasonic 30min is mixed them thoroughly uniformly；
Dye solution: weighing N719 powder 50mg, and N719 is added to absolute ethanol by dehydrated alcohol 30ml, sufficiently dissolves,
It is protected from light stirring 12h.It takes the dye solution of above-mentioned preparation to be put into brown glass ware, FTO substrate is then entered into the brown glass
It in ware, is protected from light and is sensitized 3h at 60 DEG C, take out, be then packaged together to electrode and the light anode, encapsulating material is using heat-sealing
Film encapsulates aperture, it is quick to form improvement type dye of the invention for connecting wire by electrolyte from the aperture injection to electrode one end
Change solar battery.
Preferably, in FTO substrate, when the tungsten oxide nanometer line length by thermal oxidation method growth is at 5~20 μm, diameter
70nm, density 107Root/cm2, dye-sensitized solar cells of the present invention are energy conversion devices, and performance test exists
It is tested for the property under the standard spectrum of AM1.5G, the shorted devices current density about 15.21mA/cm2, open-circuit voltage is about
0.74V, photovoltaic energy conversion efficiency is up to 18.3%；Its current attenuation is placed in an atmosphere less than 5% after duplicate measurements 500h
After 30 days, its energy conversion efficiency decays to initial value 94% is tested；Test shows the dye sensitization of solar electricity of the program
Pond current density is higher, and photoelectric conversion efficiency is higher, and device has good stability.
By test, solar cell of the invention can efficiently realize photoelectric conversion, and reproducible, decay small,
And the lighting apparatus antifreezing effect is good, and the present invention realizes making full use of for sunlight, is effectively saved the energy.
Embodiment 2:
Embodiments herein is related to a kind of solar battery, and the solar battery is based on dye-sensitized solar cells,
The dye-sensitized solar cells are constituted by light anode, to electrode and electrolyte；The structure of the light anode is from outside to inside
FTO substrate, the tungsten oxide nano for being grown on FTO substrate surface, the glass microballoon coated on tungsten oxide nano bottom；It is described
Tungsten oxide nano is core-shell structure, and core is tungsten oxide nano, and shell is titanium oxide；Described is FTO from outside to inside to electrode
Substrate, reflective layer, Pt Catalytic Layer；Antifreezing agent normal propyl alcohol is added in the electrolyte.
Preferably, such as Fig. 1, the preparation step of the dye-sensitized solar cells is as follows:
Step 1 makes FTO substrate:
A) it cleans FTO substrate: selecting FTO electro-conductive glass as the substrate of light anode, firstly, cutting FTO electro-conductive glass, is used
The conductive one side of ultra-clean cloth wiping FTO for speckling with dish washing liquid, removes the impurity such as greasy dirt, dust existing for surface, then uses deionization
Water repeated flushing for several times, until dish washing liquid is cleaned up, is put it into ozone clean machine, ozone treatment 10min, then according to
It is cleaned by ultrasonic 30min respectively according to the sequence of acetone, ethyl alcohol, deionized water, is dried up with nitrogen gun stand-by；
B) it grows tungsten oxide nano: the metal of one layer of 150nm thickness is deposited on the surface FTO using magnetron sputtering technology
Tungsten film grows source as tungsten oxide nano, while realizing that the localization of tungsten film is grown using ceramic template, in magnetron sputtering process
Ceramic template is attached to the surface FTO, wherein the pore diameter of ceramic template is 2 μm, and spacing is 50 μm, magnetron sputtering electric current
For 2A；Tungsten oxide nano growth uses thermal oxidation process, and the FTO electro-conductive glass for being coated with tungsten film is put into thermal evaporation furnace,
Under the protection of inert gas, 400 DEG C of heat preservation 5h are taken out after natural cooling；
C) it prepares core-shell structure tungsten oxide nano: weighing the ethanol solution of 100ml, be added 1ml's
C16H36O4Ti is stirred evenly under 70 DEG C of water-baths, has the FTO electro-conductive glass of tungsten oxide nano to be put into solution growth,
11s is stood, is then quickly removed, which repeats five times, can guarantee that nanowire surface adequately superscribes
The sample of taking-up is then had core-shell structure tungsten oxide nano by shell structure to obtain the final product after 400 DEG C of annealing 1h, natural cooling
FTO substrate；
Step 2 adsorbs glass microballoon:
The glass microballoon (Glass Bead Diameter is 5~10 μm) for taking 20g to buy is cleaned with deionized water, dry, is added to
It is filtered by vacuum after magnetic agitation 20min in the hydrofluoric acid solution of 20mol/l, it is dry after being cleaned with deionized water to neutrality, it removes
Ionized water 100ml sequentially adds 2.5g sodium citrate, 2.2g ammonium sulfate and 5g nano silver particles, and ammonium hydroxide is then added and adjusts pH
Value is 6, dry glass microballoon is added in above-mentioned solution, at 60 DEG C, magnetic agitation 2h is cooled to room temperature after reaction；It will
FTO substrate obtained in step 1 with core-shell structure tungsten oxide nano immerses in above-mentioned solution, stands at 80 DEG C of water-bath
5h can form glass microballoon combination core-shell structure tungsten oxide nano-material in FTO substrate surface.
Step 3 is prepared to electrode:
The FTO electro-conductive glass for choosing size identical as light anode, then in one layer of Ag of its surface magnetic control sputtering, as reflective
Then Pt catalyst layer is deposited with a thickness of 300nm in layer, Ag again, Pt catalyst layer thickness is 50nm.
Step 4 assembles dye-sensitized solar cells:
Electrolyte apply traditional three anion electrolyte of iodine/iodine: weigh the acetonitrile solution of 100ml first, thereto plus
Entering the lithium iodide of 0.1M, 0.1M iodine, the tetrabutylammonium iodide of 0.6M 4- tert .-butylpyridine and 0.6M is protected from light ultrasonic 5min,
It dissolves it sufficiently, then weighs the nano TiO 2 nanoparticle of 8g, under 70 degrees Celsius of water-bath, TiO2 nanoparticle is added
In electrolyte solution, it is eventually adding 5ml antifreezing agent normal propyl alcohol, ultrasonic 30min is mixed them thoroughly uniformly；
Dye solution: weighing N719 powder 50mg, and N719 is added to absolute ethanol by dehydrated alcohol 30ml, sufficiently dissolves,
It is protected from light stirring 12h.It takes the dye solution of above-mentioned preparation to be put into brown glass ware, FTO substrate is then entered into the brown glass
It in ware, is protected from light and is sensitized 3h at 60 DEG C, take out, be then packaged together to electrode and the light anode, encapsulating material is using heat-sealing
Film encapsulates aperture, it is quick to form improvement type dye of the invention for connecting wire by electrolyte from the aperture injection to electrode one end
Change solar battery.
Preferably, in FTO substrate, when the tungsten oxide nanometer line length by thermal oxidation method growth is at 5~22 μm, diameter
70nm, density 108Root/cm2, dye-sensitized solar cells of the present invention are energy conversion devices, and performance test exists
It is tested for the property under the standard spectrum of AM1.5G, the shorted devices current density about 16.21mA/cm2, open-circuit voltage is about
0.74V, photovoltaic energy conversion efficiency is up to 17.4%；Its current attenuation is placed in an atmosphere less than 6% after duplicate measurements 500h
After 30 days, its energy conversion efficiency decays to initial value 94% is tested；Test shows the dye sensitization of solar electricity of the program
Pond current density is higher, and photoelectric conversion efficiency is higher, and device has good stability.
By test, solar cell of the invention can efficiently realize photoelectric conversion, and reproducible, decay small,
And the lighting apparatus antifreezing effect is good, and the present invention realizes making full use of for sunlight, is effectively saved the energy.
Embodiment 3:
Embodiments herein is related to a kind of solar battery, and the solar battery is based on dye-sensitized solar cells,
The dye-sensitized solar cells are constituted by light anode, to electrode and electrolyte；The structure of the light anode is from outside to inside
FTO substrate, the tungsten oxide nano for being grown on FTO substrate surface, the glass microballoon coated on tungsten oxide nano bottom；It is described
Tungsten oxide nano is core-shell structure, and core is tungsten oxide nano, and shell is titanium oxide；Described is FTO from outside to inside to electrode
Substrate, reflective layer, Pt Catalytic Layer；Antifreezing agent normal propyl alcohol is added in the electrolyte.
Preferably, such as Fig. 1, the preparation step of the dye-sensitized solar cells is as follows:
Step 1 makes FTO substrate:
A) it cleans FTO substrate: selecting FTO electro-conductive glass as the substrate of light anode, firstly, cutting FTO electro-conductive glass, is used
The conductive one side of ultra-clean cloth wiping FTO for speckling with dish washing liquid, removes the impurity such as greasy dirt, dust existing for surface, then uses deionization
Water repeated flushing for several times, until dish washing liquid is cleaned up, is put it into ozone clean machine, ozone treatment 10min, then according to
It is cleaned by ultrasonic 30min respectively according to the sequence of acetone, ethyl alcohol, deionized water, is dried up with nitrogen gun stand-by；
B) it grows tungsten oxide nano: the metal of one layer of 150nm thickness is deposited on the surface FTO using magnetron sputtering technology
Tungsten film grows source as tungsten oxide nano, while realizing that the localization of tungsten film is grown using ceramic template, in magnetron sputtering process
Ceramic template is attached to the surface FTO, wherein the pore diameter of ceramic template is 2 μm, and spacing is 50 μm, magnetron sputtering electric current
For 2A；Tungsten oxide nano growth uses thermal oxidation process, and the FTO electro-conductive glass for being coated with tungsten film is put into thermal evaporation furnace,
Under the protection of inert gas, 400 DEG C of heat preservation 5h are taken out after natural cooling；
C) it prepares core-shell structure tungsten oxide nano: weighing the ethanol solution of 100ml, be added 1ml's
C16H36O4Ti is stirred evenly under 70 DEG C of water-baths, has the FTO electro-conductive glass of tungsten oxide nano to be put into solution growth,
11s is stood, is then quickly removed, which repeats five times, can guarantee that nanowire surface adequately superscribes
The sample of taking-up is then had core-shell structure tungsten oxide nano by shell structure to obtain the final product after 400 DEG C of annealing 1h, natural cooling
FTO substrate；
Step 2 adsorbs glass microballoon:
The glass microballoon (Glass Bead Diameter is 5~10 μm) for taking 20g to buy is cleaned with deionized water, dry, is added to
It is filtered by vacuum after magnetic agitation 20min in the hydrofluoric acid solution of 20mol/l, it is dry after being cleaned with deionized water to neutrality, it removes
Ionized water 100ml sequentially adds 2.5g sodium citrate, 2.2g ammonium sulfate and 5g nano silver particles, and ammonium hydroxide is then added and adjusts pH
Value is 6, dry glass microballoon is added in above-mentioned solution, at 60 DEG C, magnetic agitation 2h is cooled to room temperature after reaction；It will
FTO substrate obtained in step 1 with core-shell structure tungsten oxide nano immerses in above-mentioned solution, stands at 80 DEG C of water-bath
5h can form glass microballoon combination core-shell structure tungsten oxide nano-material in FTO substrate surface.
Step 3 is prepared to electrode:
The FTO electro-conductive glass for choosing size identical as light anode, then in one layer of Ag of its surface magnetic control sputtering, as reflective
Then Pt catalyst layer is deposited with a thickness of 300nm in layer, Ag again, Pt catalyst layer thickness is 50nm.
Step 4 assembles dye-sensitized solar cells:
Electrolyte apply traditional three anion electrolyte of iodine/iodine: weigh the acetonitrile solution of 100ml first, thereto plus
Entering the lithium iodide of 0.1M, 0.1M iodine, the tetrabutylammonium iodide of 0.6M 4- tert .-butylpyridine and 0.6M is protected from light ultrasonic 5min,
It dissolves it sufficiently, then weighs the nano TiO 2 nanoparticle of 8g, under 70 degrees Celsius of water-bath, TiO2 nanoparticle is added
In electrolyte solution, it is eventually adding 5ml antifreezing agent normal propyl alcohol, ultrasonic 30min is mixed them thoroughly uniformly；
Dye solution: weighing N719 powder 50mg, and N719 is added to absolute ethanol by dehydrated alcohol 30ml, sufficiently dissolves,
It is protected from light stirring 12h.It takes the dye solution of above-mentioned preparation to be put into brown glass ware, FTO substrate is then entered into the brown glass
It in ware, is protected from light and is sensitized 3h at 60 DEG C, take out, be then packaged together to electrode and the light anode, encapsulating material is using heat-sealing
Film encapsulates aperture, it is quick to form improvement type dye of the invention for connecting wire by electrolyte from the aperture injection to electrode one end
Change solar battery.
Preferably, in FTO substrate, when the tungsten oxide nanometer line length by thermal oxidation method growth is at 5~24 μm, diameter
70nm, density 108Root/cm2, dye-sensitized solar cells of the present invention are energy conversion devices, and performance test exists
It is tested for the property under the standard spectrum of AM1.5G, the shorted devices current density about 16.21mA/cm2, open-circuit voltage is about
0.74V, photovoltaic energy conversion efficiency is up to 16.8%；Its current attenuation is placed in an atmosphere less than 6% after duplicate measurements 500h
After 30 days, its energy conversion efficiency decays to initial value 94% is tested；Test shows the dye sensitization of solar electricity of the program
Pond current density is higher, and photoelectric conversion efficiency is higher, and device has good stability.
By test, solar cell of the invention can efficiently realize photoelectric conversion, and reproducible, decay small,
And the lighting apparatus antifreezing effect is good, and the present invention realizes making full use of for sunlight, is effectively saved the energy.
Embodiment 4:
Embodiments herein is related to a kind of solar battery, and the solar battery is based on dye-sensitized solar cells,
The dye-sensitized solar cells are constituted by light anode, to electrode and electrolyte；The structure of the light anode is from outside to inside
FTO substrate, the tungsten oxide nano for being grown on FTO substrate surface, the glass microballoon coated on tungsten oxide nano bottom；It is described
Tungsten oxide nano is core-shell structure, and core is tungsten oxide nano, and shell is titanium oxide；Described is FTO from outside to inside to electrode
Substrate, reflective layer, Pt Catalytic Layer；Antifreezing agent normal propyl alcohol is added in the electrolyte.
Preferably, such as Fig. 1, the preparation step of the dye-sensitized solar cells is as follows:
Step 1 makes FTO substrate:
A) it cleans FTO substrate: selecting FTO electro-conductive glass as the substrate of light anode, firstly, cutting FTO electro-conductive glass, is used
The conductive one side of ultra-clean cloth wiping FTO for speckling with dish washing liquid, removes the impurity such as greasy dirt, dust existing for surface, then uses deionization
Water repeated flushing for several times, until dish washing liquid is cleaned up, is put it into ozone clean machine, ozone treatment 10min, then according to
It is cleaned by ultrasonic 30min respectively according to the sequence of acetone, ethyl alcohol, deionized water, is dried up with nitrogen gun stand-by；
B) it grows tungsten oxide nano: the metal of one layer of 150nm thickness is deposited on the surface FTO using magnetron sputtering technology
Tungsten film grows source as tungsten oxide nano, while realizing that the localization of tungsten film is grown using ceramic template, in magnetron sputtering process
Ceramic template is attached to the surface FTO, wherein the pore diameter of ceramic template is 2 μm, and spacing is 50 μm, magnetron sputtering electric current
For 2A；Tungsten oxide nano growth uses thermal oxidation process, and the FTO electro-conductive glass for being coated with tungsten film is put into thermal evaporation furnace,
Under the protection of inert gas, 400 DEG C of heat preservation 5h are taken out after natural cooling；
C) it prepares core-shell structure tungsten oxide nano: weighing the ethanol solution of 100ml, be added 1ml's
C16H36O4Ti is stirred evenly under 70 DEG C of water-baths, has the FTO electro-conductive glass of tungsten oxide nano to be put into solution growth,
11s is stood, is then quickly removed, which repeats five times, can guarantee that nanowire surface adequately superscribes
The sample of taking-up is then had core-shell structure tungsten oxide nano by shell structure to obtain the final product after 400 DEG C of annealing 1h, natural cooling
FTO substrate；
Step 2 adsorbs glass microballoon:
The glass microballoon (Glass Bead Diameter is 5~10 μm) for taking 20g to buy is cleaned with deionized water, dry, is added to
It is filtered by vacuum after magnetic agitation 20min in the hydrofluoric acid solution of 20mol/l, it is dry after being cleaned with deionized water to neutrality, it removes
Ionized water 100ml sequentially adds 2.5g sodium citrate, 2.2g ammonium sulfate and 5g nano silver particles, and ammonium hydroxide is then added and adjusts pH
Value is 6, dry glass microballoon is added in above-mentioned solution, at 60 DEG C, magnetic agitation 2h is cooled to room temperature after reaction；It will
FTO substrate obtained in step 1 with core-shell structure tungsten oxide nano immerses in above-mentioned solution, stands at 80 DEG C of water-bath
5h can form glass microballoon combination core-shell structure tungsten oxide nano-material in FTO substrate surface.
Step 3 is prepared to electrode:
The FTO electro-conductive glass for choosing size identical as light anode, then in one layer of Ag of its surface magnetic control sputtering, as reflective
Then Pt catalyst layer is deposited with a thickness of 300nm in layer, Ag again, Pt catalyst layer thickness is 50nm.
Step 4 assembles dye-sensitized solar cells:
Electrolyte apply traditional three anion electrolyte of iodine/iodine: weigh the acetonitrile solution of 100ml first, thereto plus
Entering the lithium iodide of 0.1M, 0.1M iodine, the tetrabutylammonium iodide of 0.6M 4- tert .-butylpyridine and 0.6M is protected from light ultrasonic 5min,
It dissolves it sufficiently, then weighs the nano TiO 2 nanoparticle of 8g, under 70 degrees Celsius of water-bath, TiO2 nanoparticle is added
In electrolyte solution, it is eventually adding 5ml antifreezing agent normal propyl alcohol, ultrasonic 30min is mixed them thoroughly uniformly；
Dye solution: weighing N719 powder 50mg, and N719 is added to absolute ethanol by dehydrated alcohol 30ml, sufficiently dissolves,
It is protected from light stirring 12h.It takes the dye solution of above-mentioned preparation to be put into brown glass ware, FTO substrate is then entered into the brown glass
It in ware, is protected from light and is sensitized 3h at 60 DEG C, take out, be then packaged together to electrode and the light anode, encapsulating material is using heat-sealing
Film encapsulates aperture, it is quick to form improvement type dye of the invention for connecting wire by electrolyte from the aperture injection to electrode one end
Change solar battery.
Preferably, in FTO substrate, when the tungsten oxide nanometer line length by thermal oxidation method growth is at 5~26 μm, diameter
90nm, density 108Root/cm2, dye-sensitized solar cells of the present invention are energy conversion devices, and performance test exists
It is tested for the property under the standard spectrum of AM1.5G, the shorted devices current density about 16.21mA/cm2, open-circuit voltage is about
0.74V, photovoltaic energy conversion efficiency is up to 15.1%；Its current attenuation is placed in an atmosphere less than 6% after duplicate measurements 500h
After 30 days, its energy conversion efficiency decays to initial value 94% is tested；Test shows the dye sensitization of solar electricity of the program
Pond current density is higher, and photoelectric conversion efficiency is higher, and device has good stability.
By test, solar cell of the invention can efficiently realize photoelectric conversion, and reproducible, decay small,
And the lighting apparatus antifreezing effect is good, and the present invention realizes making full use of for sunlight, is effectively saved the energy.
Embodiment 5:
Embodiments herein is related to a kind of solar battery, and the solar battery is based on dye-sensitized solar cells,
The dye-sensitized solar cells are constituted by light anode, to electrode and electrolyte；The structure of the light anode is from outside to inside
FTO substrate, the tungsten oxide nano for being grown on FTO substrate surface, the glass microballoon coated on tungsten oxide nano bottom；It is described
Tungsten oxide nano is core-shell structure, and core is tungsten oxide nano, and shell is titanium oxide；Described is FTO from outside to inside to electrode
Substrate, reflective layer, Pt Catalytic Layer；Antifreezing agent normal propyl alcohol is added in the electrolyte.
Preferably, such as Fig. 1, the preparation step of the dye-sensitized solar cells is as follows:
Step 1 makes FTO substrate:
A) it cleans FTO substrate: selecting FTO electro-conductive glass as the substrate of light anode, firstly, cutting FTO electro-conductive glass, is used
The conductive one side of ultra-clean cloth wiping FTO for speckling with dish washing liquid, removes the impurity such as greasy dirt, dust existing for surface, then uses deionization
Water repeated flushing for several times, until dish washing liquid is cleaned up, is put it into ozone clean machine, ozone treatment 10min, then according to
It is cleaned by ultrasonic 30min respectively according to the sequence of acetone, ethyl alcohol, deionized water, is dried up with nitrogen gun stand-by；
B) it grows tungsten oxide nano: the metal of one layer of 150nm thickness is deposited on the surface FTO using magnetron sputtering technology
Tungsten film grows source as tungsten oxide nano, while realizing that the localization of tungsten film is grown using ceramic template, in magnetron sputtering process
Ceramic template is attached to the surface FTO, wherein the pore diameter of ceramic template is 2 μm, and spacing is 50 μm, magnetron sputtering electric current
For 2A；Tungsten oxide nano growth uses thermal oxidation process, and the FTO electro-conductive glass for being coated with tungsten film is put into thermal evaporation furnace,
Under the protection of inert gas, 400 DEG C of heat preservation 5h are taken out after natural cooling；
C) it prepares core-shell structure tungsten oxide nano: weighing the ethanol solution of 100ml, be added 1ml's
C16H36O4Ti is stirred evenly under 70 DEG C of water-baths, has the FTO electro-conductive glass of tungsten oxide nano to be put into solution growth,
11s is stood, is then quickly removed, which repeats five times, can guarantee that nanowire surface adequately superscribes
The sample of taking-up is then had core-shell structure tungsten oxide nano by shell structure to obtain the final product after 400 DEG C of annealing 1h, natural cooling
FTO substrate；
Step 2 adsorbs glass microballoon:
The glass microballoon (Glass Bead Diameter is 5~10 μm) for taking 20g to buy is cleaned with deionized water, dry, is added to
It is filtered by vacuum after magnetic agitation 20min in the hydrofluoric acid solution of 20mol/l, it is dry after being cleaned with deionized water to neutrality, it removes
Ionized water 100ml sequentially adds 2.5g sodium citrate, 2.2g ammonium sulfate and 5g nano silver particles, and ammonium hydroxide is then added and adjusts pH
Value is 6, dry glass microballoon is added in above-mentioned solution, at 60 DEG C, magnetic agitation 2h is cooled to room temperature after reaction；It will
FTO substrate obtained in step 1 with core-shell structure tungsten oxide nano immerses in above-mentioned solution, stands at 80 DEG C of water-bath
5h can form glass microballoon combination core-shell structure tungsten oxide nano-material in FTO substrate surface.
Step 3 is prepared to electrode:
The FTO electro-conductive glass for choosing size identical as light anode, then in one layer of Ag of its surface magnetic control sputtering, as reflective
Then Pt catalyst layer is deposited with a thickness of 300nm in layer, Ag again, Pt catalyst layer thickness is 50nm.
Step 4 assembles dye-sensitized solar cells:
Electrolyte apply traditional three anion electrolyte of iodine/iodine: weigh the acetonitrile solution of 100ml first, thereto plus
Entering the lithium iodide of 0.1M, 0.1M iodine, the tetrabutylammonium iodide of 0.6M 4- tert .-butylpyridine and 0.6M is protected from light ultrasonic 5min,
It dissolves it sufficiently, then weighs the nano TiO 2 nanoparticle of 8g, under 70 degrees Celsius of water-bath, TiO2 nanoparticle is added
In electrolyte solution, it is eventually adding 5ml antifreezing agent normal propyl alcohol, ultrasonic 30min is mixed them thoroughly uniformly；
Dye solution: weighing N719 powder 50mg, and N719 is added to absolute ethanol by dehydrated alcohol 30ml, sufficiently dissolves,
It is protected from light stirring 12h.It takes the dye solution of above-mentioned preparation to be put into brown glass ware, FTO substrate is then entered into the brown glass
It in ware, is protected from light and is sensitized 3h at 60 DEG C, take out, be then packaged together to electrode and the light anode, encapsulating material is using heat-sealing
Film encapsulates aperture, it is quick to form improvement type dye of the invention for connecting wire by electrolyte from the aperture injection to electrode one end
Change solar battery.
Preferably, in FTO substrate, when the tungsten oxide nanometer line length by thermal oxidation method growth is at 5~10 μm, diameter
90nm, density 108Root/cm2, dye-sensitized solar cells of the present invention are energy conversion devices, and performance test exists
It is tested for the property under the standard spectrum of AM1.5G, the shorted devices current density about 16.21mA/cm2, open-circuit voltage is about
0.74V, photovoltaic energy conversion efficiency is up to 13.4%；Its current attenuation is placed in an atmosphere less than 8% after duplicate measurements 500h
After 30 days, its energy conversion efficiency decays to initial value 94% is tested；Test shows the dye sensitization of solar electricity of the program
Pond current density is higher, and photoelectric conversion efficiency is higher, and device has good stability.
By test, solar cell of the invention can efficiently realize photoelectric conversion, and reproducible, decay small,
And the lighting apparatus antifreezing effect is good, and the present invention realizes making full use of for sunlight, is effectively saved the energy.
Those skilled in the art after considering the specification and implementing the invention disclosed here, will readily occur to of the invention its
Its embodiment.This application is intended to cover any variations, uses, or adaptations of the invention, these modifications, purposes or
Person's adaptive change follows general principle of the invention and including the undocumented common knowledge in the art of the application
Or conventional techniques.The description and examples are only to be considered as illustrative, and true scope and spirit of the invention are by following
Claim is pointed out.
It should be understood that the present invention is not limited to the precise structure already described above and shown in the accompanying drawings, and
And various modifications and changes may be made without departing from the scope thereof.The scope of the present invention is limited only by the attached claims.
Claims (1)
1. a kind of solar battery, which is characterized in that the solar battery is based on dye-sensitized solar cells, and the dyestuff is quick
Change solar cell to constitute by light anode, to electrode and electrolyte；The structure of the light anode includes FTO substrate, is grown on FTO base
The tungsten oxide nano of bottom surface, the glass microballoon for being adsorbed in tungsten oxide nano bottom；The tungsten oxide nano is nucleocapsid
Structure, core are tungsten oxide nano, and shell is titanium oxide；It is described that electrode is catalyzed for FTO substrate from outside to inside, reflective layer, Pt
Layer；Antifreezing agent normal propyl alcohol is added in the electrolyte；
The preparation step of the dye-sensitized solar cells is as follows:
Step 1 makes FTO substrate:
A) it cleans FTO substrate: select FTO electro-conductive glass as the substrate of light anode, firstly, cut FTO electro-conductive glass, with speckling with
The conductive one side of ultra-clean cloth wiping FTO of dish washing liquid, removes greasy dirt, dust impurity existing for surface, then repeatedly with deionized water
It rinses for several times, until dish washing liquid is cleaned up, puts it into ozone clean machine, ozone treatment 10min, then according to third
Ketone, ethyl alcohol, deionized water sequence be cleaned by ultrasonic 30min respectively, dried up with nitrogen gun stand-by；
B) it grows tungsten oxide nano: the metal tungsten film of one layer of 150nm thickness is deposited on the surface FTO using magnetron sputtering technology
Source is grown as tungsten oxide nano, while realizing that the localization of tungsten film is grown using ceramic template, it will pottery in magnetron sputtering process
Ceramic former plate is attached to the surface FTO, wherein the pore diameter of ceramic template is 2 μm, and spacing is 50 μm, and magnetron sputtering electric current is 2A；
Tungsten oxide nano growth uses thermal oxidation process, the FTO electro-conductive glass for being coated with tungsten film is put into thermal evaporation furnace, in indifferent gas
Under the protection of body, 400 DEG C of heat preservation 5h are taken out after natural cooling；
C) it prepares core-shell structure tungsten oxide nano: weighing the ethanol solution of 100ml, the C of 1ml is added16H36O4Ti, 70
It is stirred evenly under DEG C water-bath, there is the FTO electro-conductive glass of tungsten oxide nano to be put into solution growth, stand 11s, then quickly
It takes out, which is put into solution-standing-taking-up process and repeats five times, can guarantee that nanowire surface is adequately wrapped
Shell structure is wrapped, the sample of taking-up is then had to core-shell structure tungsten oxide nanometer to obtain the final product after 400 DEG C of annealing 1h, natural cooling
The FTO substrate of line；
Step 2 adsorbs glass microballoon:
The diameter for taking 20g to buy is that 5~10 μm of glass microballoon is cleaned with deionized water, dry, is added to the hydrogen fluorine of 20mol/l
It is filtered by vacuum after magnetic agitation 20min in acid solution, it is dry after being cleaned with deionized water to neutrality, ionized water 100ml is removed, according to
Secondary addition 2.5g sodium citrate, 2.2g ammonium sulfate and 5g nano silver particles, it is 6 that ammonium hydroxide, which is then added, and adjusts pH value, is mixed
Dry glass microballoon is added in above-mentioned mixed solution solution, and at 60 DEG C, magnetic agitation 2h is cooled to room temperature after reaction；
The FTO substrate that core-shell structure tungsten oxide nano is had obtained in step 1 is immersed in above-mentioned mixed solution, 80 DEG C of water-bath
Lower standing 5h can form glass microballoon combination core-shell structure tungsten oxide nano-material in FTO substrate surface；
Step 3 is prepared to electrode:
The FTO electro-conductive glass of identical as light anode size is chosen, then in one layer of Ag of its surface magnetic control sputtering, as reflective layer,
Then Pt catalyst layer is deposited with a thickness of 300nm in Ag again, Pt catalyst layer thickness is 50nm；
Step 4 assembles dye-sensitized solar cells:
Electrolyte applies traditional three anion electrolyte of iodine/iodine: weighing the acetonitrile solution of 100ml first, is added thereto
The lithium iodide of 0.1M, 0.1M iodine, the tetrabutylammonium iodide of 0.6M 4- tert .-butylpyridine and 0.6M are protected from light ultrasonic 5min, make
It is sufficiently dissolved, and then weighs the nano-TiO of 8g2Nanoparticle, under 70 degrees Celsius of water-bath, by TiO2Electricity is added in nanoparticle
In electrolyte solution, it is eventually adding 5ml antifreezing agent normal propyl alcohol, ultrasonic 30min is mixed them thoroughly uniformly；
Dye solution: weighing N719 powder 50mg, and N719 is added to absolute ethanol by dehydrated alcohol 30ml, sufficiently dissolves, is protected from light
Stir 12h；It takes the dye solution of above-mentioned preparation to be put into brown glass ware, then immerses FTO substrate in the brown glass ware,
It is protected from light and is sensitized 3h at 60 DEG C, take out, be then packaged together to electrode and the light anode, encapsulating material uses heat-sealing film, will
Electrolyte encapsulates aperture from the aperture injection to electrode one end, and connecting wire forms the dye-sensitized solar cells.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101246917A (en) * | 2007-02-14 | 2008-08-20 | 北京行者多媒体科技有限公司 | Method for intensifying light absorption of thin-film solar cell |
| CN102203890A (en) * | 2008-10-29 | 2011-09-28 | 昭和电工株式会社 | Method for manufacturing capacitor element |
| CN102231332A (en) * | 2011-03-31 | 2011-11-02 | 中国科学院安徽光学精密机械研究所 | Flexible Dye-sensitized Solar Cells (DSSCs) based on titanium dioxide nanometer rod array film and preparation method thereof |
| CN103915260A (en) * | 2012-12-26 | 2014-07-09 | 凯惠科技发展(上海)有限公司 | Flexible-titanium-based dye sensitization solar cell module, manufacturing method and power supply |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101246917A (en) * | 2007-02-14 | 2008-08-20 | 北京行者多媒体科技有限公司 | Method for intensifying light absorption of thin-film solar cell |
| CN102203890A (en) * | 2008-10-29 | 2011-09-28 | 昭和电工株式会社 | Method for manufacturing capacitor element |
| CN102231332A (en) * | 2011-03-31 | 2011-11-02 | 中国科学院安徽光学精密机械研究所 | Flexible Dye-sensitized Solar Cells (DSSCs) based on titanium dioxide nanometer rod array film and preparation method thereof |
| CN103915260A (en) * | 2012-12-26 | 2014-07-09 | 凯惠科技发展(上海)有限公司 | Flexible-titanium-based dye sensitization solar cell module, manufacturing method and power supply |
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| "Monoclinic WO3 nanorods–rutile TiO2 nanoparticles core–shell interface for efficient DSSCs";ShoyebMohamad F. Shaikh et al;《Dalton Transactions》;20130531;第42卷(第28期);第10085-10088页 |
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