CN105355712A - Silicon-based solar cell and preparation method thereof - Google Patents
Silicon-based solar cell and preparation method thereof Download PDFInfo
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- CN105355712A CN105355712A CN201510723915.XA CN201510723915A CN105355712A CN 105355712 A CN105355712 A CN 105355712A CN 201510723915 A CN201510723915 A CN 201510723915A CN 105355712 A CN105355712 A CN 105355712A
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- ultrasonic vibration
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- 239000010703 silicon Substances 0.000 title claims abstract description 36
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 36
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 85
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 85
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- 239000011521 glass Substances 0.000 claims abstract description 13
- BFMKFCLXZSUVPI-UHFFFAOYSA-N ethyl but-3-enoate Chemical group CCOC(=O)CC=C BFMKFCLXZSUVPI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 84
- 239000000463 material Substances 0.000 claims description 70
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 69
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 63
- 238000003756 stirring Methods 0.000 claims description 61
- 239000000377 silicon dioxide Substances 0.000 claims description 42
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 40
- 238000013019 agitation Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000012153 distilled water Substances 0.000 claims description 27
- 239000002244 precipitate Substances 0.000 claims description 22
- 229920001577 copolymer Polymers 0.000 claims description 21
- 235000019441 ethanol Nutrition 0.000 claims description 18
- 238000009413 insulation Methods 0.000 claims description 16
- LCJHLOJKAAQLQW-UHFFFAOYSA-N acetic acid;ethane Chemical compound CC.CC(O)=O LCJHLOJKAAQLQW-UHFFFAOYSA-N 0.000 claims description 15
- 150000002148 esters Chemical class 0.000 claims description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 230000000149 penetrating effect Effects 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000007766 curtain coating Methods 0.000 claims description 5
- 239000002313 adhesive film Substances 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 150000003376 silicon Chemical class 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 3
- 229910009372 YVO4 Inorganic materials 0.000 abstract 4
- 239000003292 glue Substances 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000001033 granulometry Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
- H01L31/055—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means where light is absorbed and re-emitted at a different wavelength by the optical element directly associated or integrated with the PV cell, e.g. by using luminescent material, fluorescent concentrators or up-conversion arrangements
-
- 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
- Y02E10/52—PV systems with concentrators
-
- 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
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a silicon-based solar cell. The silicon-based solar cell is composed of a silicon-based cell panel, a piece of transparent glass covering the silicon-based cell panel, and a photo-conversion glue layer. The photo-conversion glue layer is an ethyl vinyl acetate light-transmission polymer filled with a red-light fluorescence composition. The red-light fluorescence composition is a YVO4:Eu3+, Sr2+@YVO4: EU3+, Bi3+ or YVO4:Eu3+, Sr2+@YVO4:EU3+, Bi3+@Ag@SiO2 red-light fluorescence composition. The invention further discloses a preparation method of the silicon-based solar cell. The silicon-based solar cell is made of the nano-level red-light fluorescence composition, and possibilities are created for realizing the silicon-based solar cell high in efficiency.
Description
Technical field
The present invention relates to area of solar cell, particularly relate to a kind of silica-based solar cell and preparation method thereof.
Background technology
The design of silica-based solar cell starts from mid-term in 20th century, more precisely the sixties in 20th century, and people developed near-earth cosmic space energetically at that time.The positive advocate of silica-based solar cell is the scientists and engineers of the U.S., Russia and Japan.These initial achievements in research are edited and recorded in symposium (please refer to " semicoductor radiating power conversion " 408 pages, Moscow, foreign document publishing house, nineteen fifty-nine).Following division has been carried out: 1. photoelectricity radiation energy converter according to initial classification people; 2. thermoelectricity emittance transducer; And 3. semiconductor electromagnetic radiation converters.
Theory calculate shows, the limit photoelectric conversion rate of traditional silicon battery is 29%, so only be difficult to improve its energy conversion efficiency further by the improvement of material treatment processes.Solar cell expert B.S.Richards once pointed out, following photoelectric conversion efficiency improves further modulates the solar spectrum mainly relied on input.Because Si semiconductor has fixing band gap (1.12eV), traditional crystal-silicon solar cell cannot absorb the natural solar energy of conversion completely.The energy arriving the solar infrared spectrum district on ground accounts for 50% of whole solar spectrum energy, but the sunlight only having wavelength to be less than 1100nm could realize opto-electronic conversion in silicon crystal, wavelength be greater than ultraviolet light that the infrared light of 1100nm and wavelength be less than 400nm all cannot utilize by silicon solar cell.Conversion or down-conversion luminescent material in utilization, can modulate the solar spectrum of input, realize the utilization of silicon solar cell to all band sunlight, theory calculate shows: under conventional solar irradiance (AM1.5), and in utilization, the limit conversion efficiency of silicon solar cell can be improved more than 10% by conversion or lower conversion luminescence.
Summary of the invention
In order to solve above-mentioned the deficiencies in the prior art, the invention provides a kind of silica-based solar cell, it adopts nano level ruddiness fluorescent composition, creates possibility for realizing High-efficiency silicon based solar battery.Present invention also offers a kind of preparation method of silica-based solar cell.
Technical problem to be solved by this invention is achieved by the following technical programs:
A kind of silica-based solar cell, this silica-based solar cell transforms glue-line by a silicon based cells plate, the clear glass covering this silicon based cells plate and light between described silicon based cells plate and clear glass, and it is the ethyl vinyl acetate light penetrating copolymer being filled with ruddiness fluorescent composition that this light transforms glue-line; Described ruddiness fluorescent composition is YVO
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+or YVO
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+agSiO
2ruddiness fluorescent composition.
A kind of preparation method of silica-based solar cell, comprise the steps: to make respectively to use up conversion glue-line, between lower floor's backboard and silicon based cells plate, use EVA adhesive film as encapsulating film between upper strata transparent glass substrate and silicon based cells plate, put into vacuum laminator, temperature 135 ~ 150 DEG C, vacuumize 5 minutes, pressurize 10 ~ 15 minutes, moulding pressure 0.5 ~ 1.0kg/cm2, layers of material is bonded as one by encapsulating film, becomes silica-based solar cell; Wherein, it is the ethyl vinyl acetate light penetrating copolymer being filled with ruddiness fluorescent composition that this light transforms glue-line, and described ruddiness fluorescent composition is YVO
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+or YVO
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+agSiO
2ruddiness fluorescent composition.
The present invention has following beneficial effect: battery proposed by the invention has the substantive parameter increased.In silica-based solar cell proposed by the invention, its range of voltage values improves 24 ~ 30%, and short-circuit current value increases simultaneously, and the silica-based solar cell of its unit are has higher power.
Accompanying drawing explanation
Fig. 1 represents the figure by the determination data of the domain size distribution of the different fluorescent material obtained, and wherein, 1-1 is that embodiment 1 step 3 obtains YVO
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+the particle size distribution data figure of nucleocapsid fluorescent material; 1-2 is that embodiment 1 step 4 obtains YVO
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+the particle size distribution data figure of ruddiness fluorescent composition; 1-3 is obtained NaYF
4: Yb
3+, Er
3+the particle size distribution data figure of nano-phosphor;
Fig. 2 represents the excitation spectrum of fluorescent material 620nm supervisory wavelength that embodiment 1 to 5 and comparative example 1,2 obtain and the emission spectrum of 365nm excitation wavelength; Wherein 2-1 to 2-7 represents embodiment 1 to embodiment 5 and the spectrogram corresponding to comparative example 1,2 respectively;
Fig. 3 represents obtained NaYF
4: Yb
3+, Er
3+nano-phosphor is at the emission spectrum of 980nm excitation wavelength.
Embodiment
Below in conjunction with drawings and Examples, the present invention will be described in detail.
Embodiment 1
One, YVO is prepared
4: Eu
3+, Sr
2+nano-phosphor
(1) by 1.2mmolNa
3vO
412H
2o is dissolved in the mixed solution containing 5ml ethylene glycol and 2ml distilled water; (2) by above-mentioned solution limit ultrasonic agitation (80KHz ultrasonic vibration and 300r/min centrifugal speed stir), dropwise instillation contains the Y (NO of the certain proportioning of 1.5mmol below
3)
36H
2o, Eu (NO
3)
3, Sr (NO
3)
2(0.9:0.03:0.07) in 8ml ethylene glycol solution, then ultrasonic agitation (80KHz ultrasonic vibration and 300r/min centrifugal speed stir) 10min clarifies to solution, adds 20ml distilled water; (3) reaction solution is poured in the polytetrafluoroethyllining lining autoclave that volume is 50ml, under vacuum conditions, 200
oinsulation reaction 1h under C, is down to 150
oinsulation reaction 1h under C, after reaction terminates, is cooled to room temperature.Gained suspension is poured out, centrifugal and with acetone clean 3 times obtain white precipitates; (4) this is deposited in 90
odry 5h under C, obtains the Y of average grain diameter 10 ~ 15nm
0.9vO
4: Eu
3+ 0.03, Sr
2+ 0.07nano-phosphor; (5) to Y
0.9vO
4: Eu
3+ 0.03, Sr
2+ 0.07nano-phosphor carries out 500 DEG C of vacuum heat 1h(and is rapidly heated, and heat-treats under preferably fluorescent material being in this annealing temperature when temperature reaches 500 DEG C again), the Y of average grain diameter 20 ~ 30nm after acquisition heat treatment
0.9vO
4: Eu
3+ 0.03, Sr
2+ 0.07nano-phosphor.
Two, YVO is prepared
4: Eu
3+, Bi
3+nano-phosphor
(1) by 1.2mmolNa
3vO
412H
2o is dissolved in the mixed solution containing 5ml ethylene glycol and 2ml distilled water; (2) above-mentioned solution limit ultrasonic agitation (80KHz ultrasonic vibration and 300r/min centrifugal speed stir) limit is dropwise instilled the Y (NO containing the certain proportioning of 1.5mmol
3)
36H
2o, Eu (NO
3)
3, Bi (NO
3)
3(0.87:0.03:0.1) in 8ml ethylene glycol solution, then ultrasonic agitation (80KHz ultrasonic vibration and 300r/min centrifugal speed stir) 10min clarifies to solution, adds 20ml distilled water; (3) reaction solution is poured in the polytetrafluoroethyllining lining autoclave that volume is 50ml, under vacuum conditions, 180
oinsulation reaction 1.5h under C, after reaction terminates, is cooled to room temperature.Gained suspension is poured out, centrifugal and with acetone clean 3 times obtain white precipitates; (4) this is deposited in 90
odry 5h under C, obtains the Y that average grain diameter is about 10nm
0.87vO
4: Eu
3+ 0.03, Bi
3+ 0.1nano-phosphor.
Three, YVO is prepared
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+nucleocapsid fluorescent material
(1) pre-dispersed: to take the heat treated YVO of 0.1g
4: Eu
3+, Sr
2+nano-phosphor is placed in 10ml ethanol, and carries out ultrasonic agitation (100KHz ultrasonic vibration and 1000r/min centrifugal speed stir) dispersion 30min, obtained solution A; Take 0.008gYVO
4: Eu
3+, Bi
3+nano-phosphor is placed in 10ml ethanol, and carries out ultrasonic agitation (80KHz ultrasonic vibration and 1000r/min centrifugal speed stir) dispersion 15min, obtained solution B; (2) limit ultrasonic agitation (60KHz ultrasonic vibration and 500r/min centrifugal speed stir) solution A, limit dropwise instills solution B; Continue ultrasonic agitation (50KHz ultrasonic vibration and 100r/min centrifugal speed stir) 5min and leave standstill 5min again, centrifugal and clean 3 times with acetone and obtain white precipitates; (4) this is deposited in 90
odry 5h under C, obtains the YVO of average grain diameter 40 ~ 60nm
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+nucleocapsid fluorescent material.
Four, YVO is prepared
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+ruddiness fluorescent composition
(1) nucleocapsid fluorescent material ultrasonic agitation (100KHz ultrasonic vibration and 1000r/min centrifugal speed stir) is scattered in ethanol, obtained solution C; Add a certain proportion of (4:1) water and ammoniacal liquor afterwards, the mass ratio adding tetraethoxysilane and nucleocapsid fluorescent material after stirring is 1.5:1, and adjust ph is 9, and reaction temperature is 20 DEG C, reacts 5 hours; Carry out centrifugal and clean 3 acquisition white precipitates with acetone; This is deposited in 90
odry 5h under C, to obtain being coated with SiO
2nucleocapsid fluorescent material; (2) this is coated with SiO
2nucleocapsid fluorescent material be placed in argon gas atmosphere under carry out 800 DEG C of heat treatment 1h, obtain fluorescent material compound; (3) the fluorescent material compound of step (2) is immersed in ultrasonic 1h in hydrofluoric acid, removes silicon dioxide, centrifugal and dry, obtain the YVO of average grain diameter 60 ~ 80nm
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+ruddiness fluorescent composition.
Embodiment 2
On basis based on embodiment 1, by the YVO in step 3
4: Eu
3+, Sr
2+with YVO
4: Eu
3+, Bi
3+weight ratio change 1:0.5 into, all the other are identical with embodiment 1.
Embodiment 3
On basis based on embodiment 1, by the YVO in step 3
4: Eu
3+, Sr
2+with YVO
4: Eu
3+, Bi
3+weight ratio change 1:0.001 into, all the other are identical with embodiment 1.
Embodiment 4
One, YVO is prepared
4: Eu
3+, Sr
2+nano-phosphor
(1) by 1.2mmolNa
3vO
412H
2o is dissolved in the mixed solution containing 5ml ethylene glycol and 2ml distilled water; (2) by above-mentioned solution limit ultrasonic agitation (80KHz ultrasonic vibration and 300r/min centrifugal speed stir), dropwise instillation contains the Y (NO of the certain proportioning of 1.5mmol below
3)
36H
2o, Eu (NO
3)
3, Sr (NO
3)
2(0.9:0.03:0.07) in 8ml ethylene glycol solution, then ultrasonic agitation (80KHz ultrasonic vibration and 300r/min centrifugal speed stir) 10min clarifies to solution, adds 20ml distilled water; (3) reaction solution is poured in the polytetrafluoroethyllining lining autoclave that volume is 50ml, under vacuum conditions, 200
oinsulation reaction 1h under C, is down to 150
oinsulation reaction 1h under C, after reaction terminates, is cooled to room temperature.Gained suspension is poured out, centrifugal and with acetone clean 3 times obtain white precipitates; (4) this is deposited in 90
odry 5h under C, obtains the Y of average grain diameter 10 ~ 15nm
0.9vO
4: Eu
3+ 0.03, Sr
2+ 0.07nano-phosphor; (5) to Y
0.9vO
4: Eu
3+ 0.03, Sr
2+ 0.07nano-phosphor carries out 500 DEG C of vacuum heat 1h(and is rapidly heated, and heat-treats under preferably fluorescent material being in this annealing temperature when temperature reaches 500 DEG C again), the Y of average grain diameter 20 ~ 30nm after acquisition heat treatment
0.9vO
4: Eu
3+ 0.03, Sr
2+ 0.07nano-phosphor.
Two, YVO is prepared
4: Bi
3+nano-phosphor
(1) by 1.2mmolNa
3vO
412H
2o is dissolved in the mixed solution containing 5ml ethylene glycol and 2ml distilled water; (2) above-mentioned solution limit ultrasonic agitation (80KHz ultrasonic vibration and 300r/min centrifugal speed stir) limit is dropwise instilled the Y (NO containing the certain proportioning of 1.5mmol
3)
36H
2o, Bi (NO
3)
3(0.87:0.1) in 8ml ethylene glycol solution, then ultrasonic agitation (80KHz ultrasonic vibration and 300r/min centrifugal speed stir) 10min clarifies to solution, adds 20ml distilled water; (3) reaction solution is poured in the polytetrafluoroethyllining lining autoclave that volume is 50ml, under vacuum conditions, 180
oinsulation reaction 1.5h under C, after reaction terminates, is cooled to room temperature.Gained suspension is poured out, centrifugal and with acetone clean 3 times obtain white precipitates; (4) this is deposited in 90
odry 5h under C, obtains the Y that average grain diameter is about 10nm
0.87vO
4: Bi
3+ 0.1nano-phosphor.
Three, YVO is prepared
4: Eu
3+, Sr
2+yVO
4: Bi
3+nucleocapsid fluorescent material
(1) pre-dispersed: to take the heat treated YVO of 0.1g
4: Eu
3+, Sr
2+nano-phosphor is placed in 10ml ethanol, and carries out ultrasonic agitation (100KHz ultrasonic vibration and 1000r/min centrifugal speed stir) dispersion 30min, obtained solution A; Take 0.008gYVO
4: Bi
3+nano-phosphor is placed in 10ml ethanol, and carries out ultrasonic agitation (80KHz ultrasonic vibration and 1000r/min centrifugal speed stir) dispersion 15min, obtained solution B1; (2) limit ultrasonic agitation (60KHz ultrasonic vibration and 500r/min centrifugal speed stir) solution A, limit dropwise instills solution B 1; Continue ultrasonic agitation (50KHz ultrasonic vibration and 100r/min centrifugal speed stir) 5min and leave standstill 5min again, centrifugal and clean 3 times with acetone and obtain white precipitates; (4) this is deposited in 90
odry 5h under C, obtains the YVO of average grain diameter 40 ~ 60nm
4: Eu
3+, Sr
2+yVO
4: Bi
3+nucleocapsid fluorescent material.
Four, YVO is prepared
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+nucleocapsid fluorescent material
(1) by 0.05mmolEu (NO
3)
36H
2o ultrasonic disperse in 15ml ethanol solution, by YVO obtained for step 3
4: Eu
3+, Sr
2+yVO
4: Bi
3+nucleocapsid fluorescent material presoma is dispersed in above-mentioned solution; (2) (60KHz ultrasonic vibration and 500r/min centrifugal speed stir) after ultrasonic agitation 60min, reaction solution is left standstill 24h, ion exchange process is fully carried out.Wherein, Eu (NO
3)
36H
2the amount of O is according to chemical formula Y
(0.9-x)vO
4: Eu
3+ (x), Bi
3+ (0.1)determine, preferably excessive a little.After reaction terminates, centrifugal, and wash 3 acquisition white precipitates with absolute ethyl alcohol and distilled water.Finally, 90
ounder C, dry 5h, obtains YVO
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+nucleocapsid fluorescent material.
Five, YVO is prepared
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+ruddiness fluorescent composition
(1) nucleocapsid fluorescent material ultrasonic agitation (100KHz ultrasonic vibration and 1000r/min centrifugal speed stir) is scattered in ethanol, obtained solution C; Add a certain proportion of (4:1) water and ammoniacal liquor afterwards, the mass ratio adding tetraethoxysilane and nucleocapsid fluorescent material after stirring is 1.5:1, and adjust ph is 9, and reaction temperature is 20 DEG C, reacts 5 hours; Carry out centrifugal and clean 3 acquisition white precipitates with acetone; This is deposited in 90
odry 5h under C, to obtain being coated with SiO
2nucleocapsid fluorescent material; (2) this is coated with SiO
2nucleocapsid fluorescent material be placed in argon gas atmosphere under carry out 800 DEG C of heat treatment 1h, obtain fluorescent material compound; (3) the fluorescent material compound of step (2) is immersed in ultrasonic 1h in hydrofluoric acid, removes silicon dioxide, centrifugal and dry, obtain the YVO of average grain diameter 60 ~ 80nm
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+ruddiness fluorescent composition.
Embodiment 5
On basis based on embodiment 1 or 4, coated one deck AgSiO again after the ruddiness fluorescent composition prepared
2nanometer film, specifically comprises the steps:
(1), under room temperature, be that the polyvinylpyrrolidone of 10000 is dissolved in 30ml ethylene glycol by 6g mean molecule quantity, add 0.25gAgNO while stirring
3until formation clear solution, solution is placed in autoclave, is warming up to 130 DEG C and is incubated 30min, after being cooled to room temperature, after centrifugation, obtain quantum dot nano aluminium powder;
(2) above-mentioned for 0.15g obtained Nano Silver powder ultrasonic agitation 30min(100KHz ultrasonic vibration and 1000r/min centrifugal speed are stirred) be scattered in 30ml absolute ethyl alcohol and 10ml distilled water; Be that the ammoniacal liquor of 28% and the tetraethoxysilane TEOS of 0.15ml add in above-mentioned dispersion soln by 1.5ml mass fraction, at 20 DEG C, fully stir 4h; Carry out centrifugal and with distilled water and washes of absolute alcohol 3 times, and 80
odry 3h under C, to obtain being coated with SiO
2the AgSiO of average grain diameter about 10 nanometer
2-nanometer powder;
(3) take 0.1g ruddiness fluorescent composition and be placed in 10ml ethanol, and carry out ultrasonic agitation (100KHz ultrasonic vibration and 1000r/min centrifugal speed stir) dispersion 30min, obtained solution A1; Take 0.005gAgSiO
2-nanometer powder is placed in 10ml ethanol, and carries out ultrasonic agitation (80KHz ultrasonic vibration and 1000r/min centrifugal speed stir) dispersion 15min, obtained solution B2; Limit ultrasonic agitation (60KHz ultrasonic vibration and 500r/min centrifugal speed stir) solution A 1, limit dropwise instills solution B 2; Continue ultrasonic agitation mixed solution 5min(50KHz ultrasonic vibration and 100r/min centrifugal speed to stir) leave standstill 5min again, centrifugal and clean 3 times with acetone, and 90
odry 4h under C, obtains the YVO of average grain diameter 70 ~ 80nm
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+agSiO
2ruddiness fluorescent composition.
Comparative example 1
One, YVO is prepared
4: Eu
3+, Sr
2+nano-phosphor
(1) by 1.2mmolNa
3vO
412H
2o is dissolved in the mixed solution containing 5ml ethylene glycol and 2ml distilled water; (2) by above-mentioned solution limit ultrasonic agitation (80KHz ultrasonic vibration and 300r/min centrifugal speed stir), dropwise instillation contains the Y (NO of the certain proportioning of 1.5mmol below
3)
36H
2o, Eu (NO
3)
3, Sr (NO
3)
2(0.9:0.03:0.07) in 8ml ethylene glycol solution, then ultrasonic agitation (80KHz ultrasonic vibration and 300r/min centrifugal speed stir) 10min clarifies to solution, adds 20ml distilled water; (3) reaction solution is poured in the polytetrafluoroethyllining lining autoclave that volume is 50ml, under vacuum conditions, 200
oinsulation reaction 1h under C, is down to 150
oinsulation reaction 1h under C, after reaction terminates, is cooled to room temperature.Gained suspension is poured out, centrifugal and with acetone clean 3 times obtain white precipitates; (4) this is deposited in 90
odry 5h under C, obtains the Y of average grain diameter 10 ~ 20nm
0.9vO
4: Eu
3+ 0.03, Sr
2+ 0.07nano-phosphor; (5) to Y
0.9vO
4: Eu
3+ 0.03, Sr
2+ 0.07nano-phosphor carries out 500 DEG C of vacuum heat 1h(and is rapidly heated, and heat-treats under preferably fluorescent material being in this annealing temperature when temperature reaches 500 DEG C again), the Y of average grain diameter 20 ~ 30nm after acquisition heat treatment
0.9vO
4: Eu
3+ 0.03, Sr
2+ 0.07nano-phosphor.
Two, YVO is prepared
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+nucleocapsid fluorescent material
By the Y obtained by the first step
0.9vO
4: Eu
3+ 0.03, Sr
2+ 0.07fluorescent material (1.6mmol) is dispersed in 10ml ethylene glycol solution, and according to R value (nucleocapsid mol ratio, i.e. R=YVO
4: Eu
3+, Ba
2+/ YVO
4: Eu
3+, Bi
3+) calculate, by the Y (NO of certain molar weight
3)
36H
2o, Eu (NO
3)
3, Bi (NO
3)
35H
2o(mol ratio is 0.87:0.03:0.1) add in above-mentioned solution, and ultrasonic vibration 20min; (2) 1.2mmolNa
3vO
412H
2o adds in the mixed solution containing 5ml ethylene glycol and 2ml distilled water, dropwise instills in (1) gained solution while stirring, add 20ml distilled water after stirring 5min after dissolving completely; (3) gained reaction solution is poured in the polytetrafluoroethyllining lining autoclave that volume is 50ml (compactedness 70%), 200
ounder C, isothermal holding 2h, after reaction terminates, cools to room temperature with the furnace.Gained suspension is poured out, centrifugal and with acetone clean 3 times obtain white precipitates; (4) finally this is deposited in 80
ounder C, dry 8h, obtains YVO
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+nano-phosphor.
Three, YVO is prepared
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+ruddiness fluorescent composition
(1) nucleocapsid fluorescent material ultrasonic agitation (100KHz ultrasonic vibration and 1000r/min centrifugal speed stir) is scattered in ethanol, obtained solution C; Add a certain proportion of (4:1) water and ammoniacal liquor afterwards, the mass ratio adding tetraethoxysilane and nucleocapsid fluorescent material after stirring is 1.5:1, and adjust ph is 9, and reaction temperature is 20 DEG C, reacts 5 hours; Carry out centrifugal and clean 3 acquisition white precipitates with acetone; This is deposited in 90
odry 5h under C, to obtain being coated with SiO
2nucleocapsid fluorescent material; (2) this is coated with SiO
2nucleocapsid fluorescent material be placed in argon gas atmosphere under carry out 800 DEG C of heat treatment 1h, obtain fluorescent material compound; (3) the fluorescent material compound of step (2) is immersed in ultrasonic 1h in hydrofluoric acid, removes silicon dioxide, centrifugal and dry, obtain ruddiness fluorescent composition.
Comparative example 2
On basis based on embodiment 1, remove step 3, and in step 4, by heat treated for 1g YVO
4: Eu
3+, Sr
2+nano-phosphor and 0.05gYVO
4: Eu
3+, Bi
3+nano-phosphor mixing ultrasonic agitation (100KHz ultrasonic vibration and 1000r/min centrifugal speed stir) is scattered in ethanol, obtained solution C; All the other are identical with embodiment 1.
Performance test analysis:
The ruddiness fluorescent composition that embodiment 1 is obtained carries out XRD diffraction, bragg peak positions all in diffraction pattern, relative intensity all with YVO
4standard card (JCPDS17-0341) is consistent, can be characterized by pure Tetragonal YVO
4crystal structure, does not find other assorted peaks.
Average granulometry: the dispersion liquid obtained with ultrasonic homogenizer process, uses laser diffraction formula particle size distribution device (Shimadzu Seisakusho Ltd.'s system " SALD-7000 ") to measure average grain diameter.Average granulometry: the dispersion liquid obtained with ultrasonic homogenizer process, uses laser diffraction formula particle size distribution device (Shimadzu Seisakusho Ltd.'s system " SALD-7000 ") to measure average grain diameter.As can be seen from Figure 1, the YVO of embodiment 1 step 3 acquisition
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+nucleocapsid fluorescent material average grain diameter is 40 ~ 60nm; Embodiment 1 step 4 obtains ruddiness fluorescent composition average grain diameter 60 ~ 80nm, and nucleocapsid fluorescent material is carried out SiO
2remove again after coated annealing, can effectively prevent fluorescent material agglomeration from occurring and particle increase, the basic average grain diameter keeping ruddiness fluorescent composition.
As can be seen from Figure 2, comparative example 1 ruddiness fluorescent composition absorbs with certain broadening, and the band edge of absorption band is to long wavelength's red shift, but it is not very strong in the absorption of the ultraviolet region of short wavelength; Comparative example 2 ruddiness fluorescent composition compares ratio the last 1 in the absorption in short UV light district; Embodiment 1 to 5 ruddiness fluorescent composition absorption band has certain broadening, not only the band edge of absorption band is to long wavelength's red shift, in short UV light district, also there is good absorption at it simultaneously, particularly embodiment 5, absorbing comparatively other embodiments at ultraviolet region absorbs the strongest, is also the strongest equally at the emission peak of 620nm wavelength.
A kind of silica-based solar cell, this silica-based solar cell transforms glue-line by a silicon based cells plate, the clear glass covering this silicon based cells plate and light between described silicon based cells plate and clear glass, it is the ethyl vinyl acetate light penetrating copolymer being filled with ruddiness fluorescent composition that this light transforms glue-line, and this ruddiness fluorescent composition described is YVO
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+or YVO
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+agSiO
2ruddiness fluorescent composition.
Described light conversion layer is composed of the following components according to mass fraction: ethane-acetic acid ethyenyl ester base co-polymer 70 ~ 80 parts, crosslinking agent 0.5 ~ 1 part, tackifier 0.05 ~ 2 part, 0.05 ~ 5 part, antioxidant and ruddiness fluorescent composition 5 ~ 7 parts.The preparation method that light of the present invention transforms glue-line is not particularly limited, such as ethane-acetic acid ethyenyl ester base co-polymer can be mixed together with other auxiliary agents with the agent of ruddiness fluorescent composition, through extruding, curtain coating, cooling, draw, the operation such as to batch and be processed into light and transform glue-line; In advance part ethane-acetic acid ethyenyl ester base co-polymer and ruddiness fluorescent composition can also be mixed and made into master batch A, mix with residual ethylene-EV-51 and other auxiliary agents thereof again, through extruding, curtain coating, cooling, drawing, the operation such as to batch and be processed into light and transform glue-line; The present invention preferably adopts master batch A method.
Because described ruddiness fluorescent composition is nano level fluorescent material, therefore, glue-line is transformed in order to described ruddiness fluorescent composition is easier to be dispersed in described light, and do not form agglomeration, make this silica-based solar cell obtain better absorbing properties, this ruddiness fluorescent composition is preferably carried out lipophile process or outside coated Si O by the present invention in advance
2nanometer film.
Embodiment 6 to 10, comparative example 3 to 6, specifically fill a prescription in table 1.
The preparation method of this silica-based solar cell, specifically comprises the steps:
One, ruddiness fluorescent composition is prepared
Two, the lipophile process of ruddiness fluorescent composition
The ruddiness fluorescent composition powder that step one is obtained joins in 50ml deionized water, solution A is formed after ultrasonic agitation (80 ~ 100KHz ultrasonic vibration and 300r/min centrifugal speed stir) dispersion 20min, take 1g stearic acid to add in 100ml n-butanol and form B solution, by A, after B solution mixing, ultrasonic agitation (80 ~ 100KHz ultrasonic vibration and 300r/min centrifugal speed stir) disperses 20min again, put into 120 DEG C of oil bath return stirrings, cool to room temperature after reaction 1h, through centrifugation, deionized water washs, oil loving ruddiness fluorescent composition is obtained after 90 DEG C of dryings.
Three, prepare light and transform glue-line
Lipophile ruddiness fluorescent composition step 2 obtained fully mixes with the ethane-acetic acid ethyenyl ester base co-polymer of half, in double screw extruder, melt extrude granulation, obtained master batch A; The ethane-acetic acid ethyenyl ester base co-polymer of master batch A and remaining half and other auxiliary agents (crosslinking agent, tackifier and antioxidant) thereof are mixed, mixture is carried out blending extrusion in an extruder, temperature controls at 100 ~ 110 DEG C, extrudate through curtain coating, cooling, draw, the operation such as to batch and be processed into light and transform glue-line.
Four, lamination obtains silica-based solar cell
The light using step 3 to obtain between upper strata transparent glass substrate and silicon based cells plate respectively transforms glue-line, uses commercially available EVA adhesive film as encapsulating film between lower floor's backboard and silicon based cells plate, put into vacuum laminator, temperature 135 ~ 150 DEG C, vacuumize 5 minutes, pressurize 10 ~ 15 minutes, moulding pressure 0.5 ~ 1.0kg/cm2, layers of material is bonded as one by encapsulating film, becomes silica-based solar cell.
Wherein, the ruddiness fluorescent composition of embodiment 6 to 10 is respectively the ruddiness fluorescent composition obtained by embodiment 1 to 5, the ruddiness fluorescent composition of comparative example 3,4 is respectively the ruddiness fluorescent composition obtained by embodiment 1, and the ruddiness fluorescent composition of comparative example 5,6 is respectively the ruddiness fluorescent composition obtained by comparative example 1,2.It should be noted that, embodiment 10 can omit oleophylic process when preparing silica-based solar cell, because its ruddiness fluorescent composition Surface coating has AgSiO
2core-shell nano film, it can improve the dispersiveness of ruddiness fluorescent composition at light conversion layer.
Present invention also offers a kind of silica-based solar cell, this silica-based solar cell transforms glue-line by a silicon based cells plate, the clear glass covering this silicon based cells plate and light between described silicon based cells plate and clear glass, and this light transforms glue-line for being filled with ruddiness fluorescent composition and NaYF
4: Yb
3+, Er
3+the ethyl vinyl acetate light penetrating copolymer of nano-phosphor, this ruddiness fluorescent composition described is YVO
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+or YVO
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+agSiO
2ruddiness fluorescent composition.
Described light conversion layer is composed of the following components according to mass fraction: ethane-acetic acid ethyenyl ester base co-polymer 70 ~ 80 parts, crosslinking agent 0.5 ~ 1 part, tackifier 0.05 ~ 2 part, 0.05 ~ 5 part, antioxidant, ruddiness fluorescent composition 5 ~ 7 parts and NaYF
4: Yb
3+, Er
3+nano-phosphor 1.5 ~ 2 parts.
Embodiment 11 to 13, specifically fills a prescription in table 1.
The preparation method of this silica-based solar cell, specifically comprises the steps:
One, ruddiness fluorescent composition is prepared, NaYF
4: Yb
3+, Er
3+nano-phosphor
The ruddiness fluorescent composition of this ruddiness fluorescent composition obtained by embodiment 1;
Described NaYF
4: Yb
3+, Er
3+the preparation method of fluorescent material is as follows:
(1) 1.8mmolY (NO is taken
3)
36H
2o, 0.17mmolYb (NO
3)
35H
2o, 0.1mmolEr (NO
3)
35H
2o, with 2mmolNaNO
3mixing is also fully dissolved in 15ml ethylene glycol and forms solution F; By 8mmolNH
4f is fully dissolved in 15ml ethylene glycol and forms solution G; Ultrasonic agitation (80KHz ultrasonic vibration and 300r/min centrifugal speed stir) solution F, G30min respectively, at continuation ultrasonic agitation (80KHz ultrasonic vibration and 300r/min centrifugal speed stir) 30min after two solution mixing; Mixed solution is poured in polytetrafluoroethyllining lining autoclave that volume is 50ml, under vacuum conditions, 180
oinsulation reaction 12h under C, is down to 150
oinsulation reaction 4h under C, after reaction terminates, is cooled to room temperature.Gained suspension is poured out, centrifugal and with distilled water and absolute ethyl alcohol clean successively 3 times obtain fluorescent material; This is deposited in 80
odry 5h under C, obtains the NaYF of average grain diameter 30 ~ 60nm
4: Yb
3+, Er
3+nano-phosphor;
(2) by above-mentioned for 0.3g obtained nano NaY F
4: Yb
3+, Er
3+phosphor powder ultrasonic agitation 30min(100KHz ultrasonic vibration and 1000r/min centrifugal speed stir) be scattered in 40ml absolute ethyl alcohol and 10ml distilled water; Be that the ammoniacal liquor of 28% and the tetraethoxysilane TEOS of 0.3ml add in above-mentioned dispersion soln by 2ml mass fraction, at 20 DEG C, fully stir 4h, obtained NaYF
4: Yb
3+, Er
3+siO
2-powder; Carry out centrifugal and obtain white precipitate 3 times with distilled water and washes of absolute alcohol; This is deposited in 90
odry 5h under C, to obtain being coated with SiO
2naYF
4: Yb
3+, Er
3+nucleocapsid fluorescent material; By this NaYF
4: Yb
3+, Er
3+siO
2nucleocapsid fluorescent material carries out 800 DEG C of heat treatment 60min under being placed in argon gas atmosphere, obtains fluorescent material compound; Fluorescent material compound is immersed in ultrasonic 1h in hydrofluoric acid, removes silicon dioxide, centrifugal and dry, obtain the NaYF of average grain diameter 40 ~ 70nm
4: Yb
3+, Er
3+nano-phosphor, its particle size determination 1-3 as shown in Figure 1, it launches corresponding characteristic peak under 980nm excitation wavelength, is particularly positioned at the highest peak of 655nm, as shown in Figure 3.
Two, ruddiness fluorescent composition and NaYF
4: Yb
3+, Er
3+the lipophile process of nano-phosphor
The ruddiness fluorescent composition powder that step one is obtained joins in 50ml deionized water, solution A is formed after ultrasonic agitation (80 ~ 100KHz ultrasonic vibration and 300r/min centrifugal speed stir) dispersion 20min, take 1g stearic acid to add in 100ml n-butanol and form B solution, by A, after B solution mixing, ultrasonic agitation (80 ~ 100KHz ultrasonic vibration and 300r/min centrifugal speed stir) disperses 20min again, put into 120 DEG C of oil bath return stirrings, cool to room temperature after reaction 1h, through centrifugation, deionized water washs, oil loving ruddiness fluorescent composition is obtained after 90 DEG C of dryings.Described NaYF
4: Yb
3+, Er
3+the oleophylic processing method of nano-phosphor, with the processing method of ruddiness fluorescent composition, does not repeat them here.
Three, prepare light and transform glue-line
The lipophile ruddiness fluorescent composition that step 2 is obtained with 30% ethane-acetic acid ethyenyl ester base co-polymer fully mix, in double screw extruder, melt extrude granulation, obtained master batch A; The lipophile NaYF obtained by step 2
4: Yb
3+, Er
3+nano-phosphor with 30% ethane-acetic acid ethyenyl ester base co-polymer fully mix, in double screw extruder, melt extrude granulation, obtained mother particle B; Master batch A and mother particle B are mixed with remaining ethane-acetic acid ethyenyl ester base co-polymer and other auxiliary agents (crosslinking agent, tackifier and antioxidant) thereof, mixture is carried out blending extrusion in an extruder, temperature controls at 100 ~ 110 DEG C, extrudate through curtain coating, cooling, draw, the operation such as to batch and be processed into light and transform glue-line.
Four, lamination obtains silica-based solar cell
The light using step 3 to obtain between upper strata transparent glass substrate and silicon based cells plate respectively transforms glue-line, uses commercially available EVA adhesive film as encapsulating film between lower floor's backboard and silicon based cells plate, put into vacuum laminator, temperature 135 ~ 150 DEG C, vacuumize 5 minutes, pressurize 10 ~ 15 minutes, moulding pressure 0.5 ~ 1.0kg/cm2, layers of material is bonded as one by encapsulating film, becomes silica-based solar cell.
If compared with general known monocrystalline silicon battery type of not adding any fluorescent material by the silica-based light energy battery transforming glue-line containing ruddiness of the present invention, namely following form can be drawn:
Conclusion as can be drawn from Table 1, monocrystaline silicon solar cell proposed by the invention has high electrical parameter, for not adding 1.24 ~ 1.3 times of any fluorescent material, its conversion efficiency exceeds 17 ~ 30%, in silica-based solar cell proposed by the invention, voltage and short-circuit current value all increase, and the silica-based solar cell of its unit are has higher power, this is the very important feature of device proposed by the invention, particularly applies two light-conversion fluorescent powder.
The above embodiment only have expressed embodiments of the present invention; it describes comparatively concrete and detailed; but therefore can not be interpreted as the restriction to the scope of the claims of the present invention; in every case the technical scheme adopting the form of equivalent replacement or equivalent transformation to obtain, all should drop within protection scope of the present invention.
Claims (7)
1. a silica-based solar cell, this silica-based solar cell transforms glue-line by a silicon based cells plate, the clear glass covering this silicon based cells plate and light between described silicon based cells plate and clear glass, and it is the ethyl vinyl acetate light penetrating copolymer being filled with ruddiness fluorescent composition that this light transforms glue-line; Described ruddiness fluorescent composition is YVO
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+or YVO
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+agSiO
2ruddiness fluorescent composition.
2. silica-based solar cell according to claim 1, it is characterized in that, described light conversion layer is composed of the following components according to mass fraction: ethane-acetic acid ethyenyl ester base co-polymer 70 ~ 80 parts, crosslinking agent 0.5 ~ 1 part, tackifier 0.05 ~ 2 part, 0.05 ~ 5 part, antioxidant and ruddiness fluorescent composition 5 ~ 7 parts; This ruddiness fluorescent composition accounts for 8.5% of this ethane-acetic acid ethyenyl ester base co-polymer total weight.
3. silica-based solar cell according to claim 1 and 2, is characterized in that, described ruddiness fluorescent composition particle diameter is 40 ~ 100nm.
4. the preparation method of a silica-based solar cell, comprise the steps: to make respectively to use up conversion glue-line, between lower floor's backboard and silicon based cells plate, use EVA adhesive film as encapsulating film between upper strata transparent glass substrate and silicon based cells plate, put into vacuum laminator, temperature 135 ~ 150 DEG C, vacuumize 5 minutes, pressurize 10 ~ 15 minutes, moulding pressure 0.5 ~ 1.0kg/cm2, layers of material is bonded as one by encapsulating film, becomes silica-based solar cell; Wherein, it is the ethyl vinyl acetate light penetrating copolymer being filled with ruddiness fluorescent composition that this light transforms glue-line, and described ruddiness fluorescent composition is YVO
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+or YVO
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+agSiO
2ruddiness fluorescent composition.
5. the preparation method of silica-based solar cell according to claim 4, it is characterized in that, described light conversion layer is composed of the following components according to mass fraction: ethane-acetic acid ethyenyl ester base co-polymer 70 ~ 80 parts, crosslinking agent 0.5 ~ 1 part, tackifier 0.05 ~ 2 part, 0.05 ~ 5 part, antioxidant and ruddiness fluorescent composition 5 ~ 7 parts; This ruddiness fluorescent composition accounts for 8.5% of this ethane-acetic acid ethyenyl ester base co-polymer total weight; Described light transforms glue-line and is obtained by following methods: fully mixed with the ethane-acetic acid ethyenyl ester base co-polymer of half by ruddiness fluorescent composition, in double screw extruder, melt extrude granulation, obtained master batch A; The ethane-acetic acid ethyenyl ester base co-polymer of master batch A and remaining half, crosslinking agent, tackifier and antioxidant are mixed, mixture is carried out blending extrusion in an extruder, temperature controls at 100 ~ 110 DEG C, extrudate through curtain coating, cooling, draw, the operation such as to batch and be processed into light and transform glue-line.
6. the preparation method of silica-based solar cell according to claim 4, is characterized in that, described YVO
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+ruddiness fluorescent composition is obtained by following methods:
One, YVO is prepared
4: Eu
3+, Sr
2+nano-phosphor
(1) by 1.2mmolNa
3vO
412H
2o is dissolved in the mixed solution containing 5ml ethylene glycol and 2ml distilled water; (2) above-mentioned solution limit 80 ~ 100KHz ultrasonic vibration and 300r/min centrifugal speed are stirred below the dropwise Y (NO of instillation containing the certain proportioning of 1.5mmol
3)
36H
2o, Eu (NO
3)
3, Sr (NO
3)
28ml ethylene glycol solution in, more simultaneously 80KHz ultrasonic vibration and 300r/min centrifugal speed stir 5 ~ 10min and clarify to solution, add 20ml distilled water; (3) reaction solution is poured in the polytetrafluoroethyllining lining autoclave that volume is 50ml, under vacuum conditions, 200
oinsulation reaction 1h under C, is down to 150
oinsulation reaction 1h under C, after reaction terminates, is cooled to room temperature; Gained suspension is poured out, centrifugal and with acetone clean 3 times obtain white precipitates; (4) this is deposited in 90
ounder C, dry 5h, obtains Y
0.9vO
4: Eu
3+ 0.03, Sr
2+ 0.07nano-phosphor; (5) to Y
0.9vO
4: Eu
3+ 0.03, Sr
2+ 0.07nano-phosphor carries out 500 DEG C of vacuum heat 1h, and after acquisition heat treatment, average grain diameter is 20 ~ 30nmY
0.9vO
4: Eu
3+ 0.03, Sr
2+ 0.07nano-phosphor;
Two, YVO is prepared
4: Eu
3+, Bi
3+nano-phosphor
(1) by 1.2mmolNa
3vO
412H
2o is dissolved in the mixed solution containing 5ml ethylene glycol and 2ml distilled water; (2) above-mentioned solution limit 80 ~ 100KHz ultrasonic vibration and 300r/min centrifugal speed stirring limit are dropwise instilled the Y (NO containing the certain proportioning of 1.5mmol
3)
36H
2o, Eu (NO
3)
3, Bi (NO
3)
38ml ethylene glycol solution in, more simultaneously 80KHz ultrasonic vibration and 300r/min centrifugal speed stir 5 ~ 10min and clarify to solution, add 20ml distilled water; (3) reaction solution is poured in the polytetrafluoroethyllining lining autoclave that volume is 50ml, under vacuum conditions, 180
oinsulation reaction 1.5h under C, after reaction terminates, is cooled to room temperature; Gained suspension is poured out, centrifugal and with acetone clean 3 times obtain white precipitates; (4) this is deposited in 90
odry 5h under C, obtaining average grain diameter is 10nmY
0.87vO
4: Eu
3+ 0.03, Bi
3+ 0.1nano-phosphor;
Three, YVO is prepared
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+nucleocapsid fluorescent material
(1) pre-dispersed: to take the heat treated YVO of 1g
4: Eu
3+, Sr
2+nano-phosphor is placed in 10ml ethanol, and disperses 30min, obtained solution A under carrying out 100KHz ultrasonic vibration and the stirring of 1000r/min centrifugal speed; Take 0.05gYVO
4: Eu
3+, Bi
3+nano-phosphor is placed in 10ml ethanol, and disperses 15min, obtained solution B under carrying out 80KHz ultrasonic vibration and the stirring of 1000r/min centrifugal speed; (2) limit 60KHz ultrasonic vibration and 500r/min centrifugal speed agitating solution A, limit dropwise instills solution B; Continue 50KHz ultrasonic vibration and 100r/min centrifugal speed to stir 5min and leave standstill 5min again, centrifugal and clean 3 times with acetone and obtain white precipitates; (4) this is deposited in 90
odry 5h under C, obtaining average grain diameter is 40 ~ 60nmYVO
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+nucleocapsid fluorescent material;
Four, YVO is prepared
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+ruddiness fluorescent composition
(1) nucleocapsid fluorescent material is scattered in ethanol under 100KHz ultrasonic vibration and 1000r/min centrifugal speed stir, obtained solution C; Additional proportion is water and the ammoniacal liquor of 4:1 afterwards, and the mass ratio adding tetraethoxysilane and nucleocapsid fluorescent material after stirring is 1.5:1, and adjust ph is 9, and reaction temperature is 20 DEG C, reacts 5 hours; Carry out centrifugal and clean 3 acquisition white precipitates with acetone; This is deposited in 90
odry 5h under C, to obtain being coated with SiO
2nucleocapsid fluorescent material; (2) this is coated with SiO
2nucleocapsid fluorescent material be placed in argon gas atmosphere under carry out 800 DEG C of heat treatment 1h, obtain fluorescent material compound; (3) the fluorescent material compound of step (2) is immersed in ultrasonic 1h in hydrofluoric acid, removes silicon dioxide, centrifugal and dry, obtain average grain diameter 60 ~ 80nm ruddiness fluorescent composition.
7. the preparation method of silica-based solar cell according to claim 4, is characterized in that, described YVO
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+ruddiness fluorescent composition is obtained by following methods:
One, YVO is prepared
4: Eu
3+, Sr
2+nano-phosphor
(1) by 1.2mmolNa
3vO
412H
2o is dissolved in the mixed solution containing 5ml ethylene glycol and 2ml distilled water; (2) above-mentioned solution limit 80 ~ 100KHz ultrasonic vibration and 300r/min are dropwise instilled the Y (NO containing the certain proportioning of 1.5mmol below
3)
36H
2o, Eu (NO
3)
3, Sr (NO
3)
28ml ethylene glycol solution in, then 80 ~ 100KHz ultrasonic vibration and 300r/min centrifugal speed stir 10min and clarify to solution, add 20ml distilled water; (3) reaction solution is poured in the polytetrafluoroethyllining lining autoclave that volume is 50ml, under vacuum conditions, 200
oinsulation reaction 1h under C, is down to 150
oinsulation reaction 1h under C, after reaction terminates, is cooled to room temperature; Gained suspension is poured out, centrifugal and with acetone clean 3 times obtain white precipitates; (4) this is deposited in 90
odry 5h under C, obtains the Y of average grain diameter 10 ~ 15nm
0.9vO
4: Eu
3+ 0.03, Sr
2+ 0.07nano-phosphor; (5) to Y
0.9vO
4: Eu
3+ 0.03, Sr
2+ 0.07nano-phosphor carries out 500 DEG C of vacuum heat 1h, the Y of average grain diameter 20 ~ 30nm after acquisition heat treatment
0.9vO
4: Eu
3+ 0.03, Sr
2+ 0.07nano-phosphor;
Two, YVO is prepared
4: Bi
3+nano-phosphor
(1) by 1.2mmolNa
3vO
412H
2o is dissolved in the mixed solution containing 5ml ethylene glycol and 2ml distilled water; (2) above-mentioned solution limit 80 ~ 100KHz ultrasonic vibration and 300r/min centrifugal speed stirring limit are dropwise instilled the Y (NO containing the certain proportioning of 1.5mmol
3)
36H
2o, Bi (NO
3)
38ml ethylene glycol solution in, then 80 ~ 100KHz ultrasonic vibration and 300r/min centrifugal speed stir 10min and clarify to solution, add 20ml distilled water; (3) reaction solution is poured in the polytetrafluoroethyllining lining autoclave that volume is 50ml, under vacuum conditions, 180
oinsulation reaction 1.5h under C, after reaction terminates, is cooled to room temperature; Gained suspension is poured out, centrifugal and with acetone clean 3 times obtain white precipitates; (4) this is deposited in 90
odry 5h under C, obtains the Y that average grain diameter is about 10nm
0.87vO
4: Bi
3+ 0.1nano-phosphor;
Three, YVO is prepared
4: Eu
3+, Sr
2+yVO
4: Bi
3+nucleocapsid fluorescent material
(1) pre-dispersed: to take the heat treated YVO of 0.1g
4: Eu
3+, Sr
2+nano-phosphor is placed in 10ml ethanol, and carries out 100KHz ultrasonic vibration and 1000r/min centrifugal speed dispersed with stirring 30min, obtained solution A; Take 0.008gYVO
4: Bi
3+nano-phosphor is placed in 10ml ethanol, and carries out 80KHz ultrasonic vibration and 1000r/min centrifugal speed dispersed with stirring 15min, obtained solution B1; (2) limit 60KHz ultrasonic vibration and 500r/min centrifugal speed agitating solution A, limit dropwise instills solution B 1; Continue ultrasonic agitation 50KHz ultrasonic vibration and 100r/min centrifugal speed to stir 5min and leave standstill 5min again, centrifugal and clean 3 times with acetone and obtain white precipitates; (4) this is deposited in 90
odry 5h under C, obtains the YVO of average grain diameter 40 ~ 60nm
4: Eu
3+, Sr
2+yVO
4: Bi
3+nucleocapsid fluorescent material;
Four, YVO is prepared
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+nucleocapsid fluorescent material
(1) by 0.05mmolEu (NO
3)
36H
2o ultrasonic disperse in 15ml ethanol solution, by YVO obtained for step 3
4: Eu
3+, Sr
2+yVO
4: Bi
3+nucleocapsid fluorescent material presoma is dispersed in above-mentioned solution; (2), after 60KHz ultrasonic vibration and 500r/min centrifugal speed stir 60min, reaction solution is left standstill 24h; After reaction terminates, centrifugal, and wash 3 acquisition white precipitates with absolute ethyl alcohol and distilled water; 90
ounder C, dry 5h, obtains YVO
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+nucleocapsid fluorescent material;
Five, YVO is prepared
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+ruddiness fluorescent composition
(1) by nucleocapsid fluorescent material 100KHz ultrasonic vibration and 1000r/min centrifugal speed dispersed with stirring in ethanol, obtained solution C; Additional proportion is water and the ammoniacal liquor of 4:1 afterwards, and the mass ratio adding tetraethoxysilane and nucleocapsid fluorescent material after stirring is 1.5:1, and adjust ph is 9, and reaction temperature is 20 DEG C, reacts 5 hours; Carry out centrifugal and clean 3 acquisition white precipitates with acetone; This is deposited in 90
odry 5h under C, to obtain being coated with SiO
2nucleocapsid fluorescent material; (2) this is coated with SiO
2nucleocapsid fluorescent material be placed in argon gas atmosphere under carry out 800 DEG C of heat treatment 1h, obtain fluorescent material compound; (3) the fluorescent material compound of step (2) is immersed in ultrasonic 1h in hydrofluoric acid, removes silicon dioxide, centrifugal and dry, obtain the YVO of average grain diameter 60 ~ 80nm
4: Eu
3+, Sr
2+yVO
4: Eu
3+, Bi
3+ruddiness fluorescent composition.
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| US20130098438A1 (en) * | 2010-06-11 | 2013-04-25 | Asahi Glass Company, Limited | Translucent laminated film and solar cell module using it |
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