CN102260041B - Super-white photovoltaic glass and preparation method and application thereof - Google Patents
Super-white photovoltaic glass and preparation method and application thereof Download PDFInfo
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- CN102260041B CN102260041B CN 201010190100 CN201010190100A CN102260041B CN 102260041 B CN102260041 B CN 102260041B CN 201010190100 CN201010190100 CN 201010190100 CN 201010190100 A CN201010190100 A CN 201010190100A CN 102260041 B CN102260041 B CN 102260041B
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Abstract
The invention provides super-white photovoltaic glass and a preparation method and application thereof. The super-white photovoltaic glass comprises substrate glass and a rare earth compound doped into the substrate glass, wherein the rare earth compound is rare earth oxide or rare earth-containing mineral; the rare earth oxide is at least one of CeO2, Sm2O3, Eu2O3, Tb2O3 and Dy2O3; and the rare earth-containing mineral comprises at least one element of Ce, Sm, Eu, Tb and Dy. The super-white photovoltaic glass can convert ultraviolet light into visible light, so that the transmittance of the visible light is enhanced; when the super-white photovoltaic glass is used for a glass cover plate of a solar cell, the conversion efficiency of the cell can be improved, generated energy is increased, and the aging of sealing materials such as ethylene-vinyl acetate (EVA) caused by the ultraviolet light can be reduced; and the preparation method of the super-white photovoltaic glass is simple, easy to operate and control and suitable for industrial production.
Description
Technical field
The invention belongs to the used for solar batteries glass art, relate in particular to a kind of ultra-white photovoltaic glass and its preparation method and application.
Background technology
The solar radiation that earth surface is accepted can satisfy 10,000 times of global energy demand, and the every square metre of radiation that is subject to every year on average in earth's surface can be produced the 1700kW.h electricity.The International Energy Agency data presentation is installed solar energy photovoltaic system in the desert in the whole world 4%, just is enough to satisfy the global energy demand.Photovoltaic is enjoyed wide development space (roof, building sides, vacant lot and desert etc.), and its potentiality are very huge, and the ratio of the renewable energy source take sun power as representative in energy structure will progressively improve.
Ultra-clear glasses claims again low iron glass, photovoltaic glass etc., be defined as the glass iron level in the industry standard " solar cell glass " and be not higher than 150ppm, glass folding 3mm standard thickness visible transmission is amounted to the direct transmittance of sunlight (300～2500nm spectral range) of 3mm standard thickness and is answered 〉=91% than answering 〉=91.5%.(have high permeability in 380～1200nm), therefore be widely used in the solar battery glass cover plate in the solar cell spectral response range just because of ultra-clear glasses.
Yet the cost of photovoltaic generation is still higher at present, and one of them important reason is because the efficiency of conversion not high (silicon single crystal and polysilicon are 15%～20%, and amorphous silicon membrane is 5～10%) of solar cell.So the various countries scientist is in the efficiency of conversion of being devoted to improve all kinds of batteries.But all kinds of solar cells are more limited to the scope of solar spectrum response, and at 380～800nm, peak value is 600nm approximately such as amorphous silicon film battery; Crystal silicon cell is at 380～1200nm, and peak value is 900nm approximately.The limited spectral response range of solar cell is that distinctive spectral losses can reduce its efficiency of conversion greatly, take the unijunction monocrystalline silicon battery of energy gap Eg=1.1ev as example, only have wavelength could be absorbed and realize opto-electronic conversion by the silicon single crystal semiconductor material less than the sunlight of 1200nm (photon energy is greater than 1.1ev), wavelength then can not be absorbed and used greater than the infrared light of 1200nm; Wavelength less than the UV-light of 380nm owing to being absorbed and can not be used to generating by battery by seal, sealing materials such as EVA (poly-vinegar ethyl ester); In addition, in the 380-1200nm sunlight scope that can be used for generating electricity, neither all photon energies all be converted to electricity, wherein some is the formal transformation with heat.So these spectral losses cause the theoretical maximum conversion efficiency of the unijunction monocrystalline silicon battery of energy gap Eg=1.1ev to be about 31%.
Summary of the invention
The object of the invention is to, a kind of absorption UV-light is provided, the ultra-white photovoltaic glass of emission visible light.
Another object of the present invention is to provide that a kind of technique is simple, the preparation method of the ultra-white photovoltaic glass that is easy to operate and control.
Further aim of the present invention is to provide the application of above-mentioned ultra-white photovoltaic glass in the solar battery glass cover plate.
In order to realize the foregoing invention purpose, technical scheme of the present invention is as follows:
A kind of ultra-white photovoltaic glass comprises host glass and the rare earth compound that is doped in the host glass, and described rare earth compound is rare earth oxide or ores containing rare earths thing, and described rare earth oxide is CeO
2, Sm
2O
3, Eu
2O
3, Tb
2O
3, Dy
2O
3In at least a, described ores containing rare earths thing is the rare-earth mineral that contains at least a element among Ce, Sm, Eu, Tb, the Dy.
And, a kind of ultra-white photovoltaic glass preparation method, the method comprises the steps:
Host glass and the rare earth compound that is doped in the host glass are heated to 1500～1600 ℃ of fusings, after clarification and cooling, adopt floating process or calendering technology to make sheet glass, then obtain described ultra-white photovoltaic glass through annealing process, described rare earth compound is rare earth oxide or ores containing rare earths thing, and described rare earth oxide is CeO
2, Sm
2O
3, Eu
2O
3, Tb
2O
3, Dy
2O
3In at least a, described ores containing rare earths thing is the rare-earth mineral that contains at least a element among Ce, Sm, Eu, Tb, the Dy.
Further, the invention provides the application of ultra-white photovoltaic glass in the solar battery glass cover plate.
Because above-mentioned ultra-white photovoltaic glass is doped in the host glass by rare earth compound and consists of, the existence of the rare earth ions such as Ce, Sm, Eu, Tb, Dy, itself does not only absorb visible light, and effectively convert UV-light to visible light, thereby strengthened the transmitance of visible light, when this ultra-white photovoltaic glass is used for the glass cover-plate of solar cell, not only can improve the efficiency of conversion of battery, increase generated energy, but also can reduce UV-light to the solarization of the seal, sealing materials such as EVA.Meanwhile, this ultra-white photovoltaic glass adopts the host glass material of high-quality and reasonably fills a prescription, so that it has higher transmitance to visible light.Among this ultra-white photovoltaic glass preparation method, only need according to prescription each component to be mixed, and heat fused, need not special equipment and environmental requirement, its preparation method technique is simple, and is easy to operate and control, and is suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is 1% (% by weight) Sm that mixes in the ultra-white photovoltaic glass in the embodiment of the invention
2O
3, and thickness of glass is 4mm, the transmittance curve of glass after the polishing both surfaces;
Fig. 2 is 1% (% by weight) Sm that mixes in the ultra-white photovoltaic glass in the embodiment of the invention
2O
3The emmission spectrum of rear glass;
Fig. 3 is 1% (% by weight) Sm that mixes in the ultra-white photovoltaic glass in the embodiment of the invention
2O
3The excitation spectrum of rear glass.
Fig. 4 is 1% (% by weight) CeO that mixes in the ultra-white photovoltaic glass in the embodiment of the invention
2With 1% (% by weight) Sm
2O
3, and thickness of glass is 4mm, the transmittance curve of glass after the polishing both surfaces;
Fig. 5 is 1% (% by weight) CeO that mixes in the ultra-white photovoltaic glass in the embodiment of the invention
2With 1% (% by weight) Sm
2O
3The emmission spectrum of rear glass;
Fig. 6 is 1% (% by weight) CeO that mixes in the ultra-white photovoltaic glass in the embodiment of the invention
2With 1% (% by weight) Sm
2O
3The excitation spectrum of rear glass.
Fig. 7 is 2% (% by weight) Eu that mixes in the ultra-white photovoltaic glass in the embodiment of the invention
2O
3, and thickness of glass is 4mm, the transmittance curve of glass after the polishing both surfaces;
Fig. 8 is 2% (% by weight) Eu that mixes in the ultra-white photovoltaic glass in the embodiment of the invention
2O
3The excitation spectrum of rear glass;
Fig. 9 is 2% (% by weight) Eu that mixes in the ultra-white photovoltaic glass in the embodiment of the invention
2O
3The emmission spectrum of rear glass;
Figure 10 is 2% (% by weight) Tb that mixes in the ultra-white photovoltaic glass in the embodiment of the invention
2O
3, and thickness of glass 4mm, the transmittance curve of glass after the polishing both surfaces;
Figure 11 is 2% (% by weight) Tb that mixes in the ultra-white photovoltaic glass in the embodiment of the invention
2O
3The excitation spectrum of rear glass;
Figure 12 is 2% (% by weight) Tb that mixes in the ultra-white photovoltaic glass in the embodiment of the invention
2O
3The emmission spectrum of rear glass;
Figure 13 is 2% (% by weight) Dy that mixes in the ultra-white photovoltaic glass in the embodiment of the invention
2O
3, and thickness of glass 4mm, the transmittance curve of glass after the polishing both surfaces;
Figure 14 is 2% (% by weight) Dy that mixes in the ultra-white photovoltaic glass in the embodiment of the invention
2O
3The excitation spectrum of rear glass;
Figure 15 is 2% (% by weight) Dy that mixes in the ultra-white photovoltaic glass in the embodiment of the invention
2O
3The emmission spectrum of rear glass.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
A kind of ultra-white photovoltaic glass that the embodiment of the invention provides comprises host glass and the rare earth compound that is doped in the host glass, and described rare earth compound is rare earth oxide or ores containing rare earths thing, and described rare earth oxide is CeO
2, Sm
2O
3, Eu
2O
3, Tb
2O
3, Dy
2O
3In at least a, described ores containing rare earths thing is for containing at least a kind of Ce, Sm, Eu, Tb, Dy element rare-earth mineral.
In the above-mentioned ultra-white photovoltaic glass, described host glass is take oxide compound as benchmark, and its component that comprises is preferably:
SiO
2 70～80wt％
Na
2O 10～20wt％
CaO 5～15wt％
MgO 0.1～5wt％
Al
2O
3 0.1～5wt％；
Describedly be doped in rare earth compound in the host glass take rare earth oxide as benchmark, balance to 100%.
In the above-mentioned ultra-white photovoltaic glass, described host glass is take oxide compound as benchmark, its component that comprises more preferably:
SiO
2 70～75wt％
Na
2O 12～15wt％
CaO 7～12wt％
MgO 2～5wt％
Al
2O
3 0.5～2wt％
Above-mentionedly be doped in rare earth compound in the host glass take rare earth oxide as benchmark, balance to 100%, wherein, described rare earth compound further preferably comprises following component:
Eu
2O
3 0.1～2wt％
Tb
2O
3 0.1～2wt％
Dy
2O
3 0.1～2wt％。
Above-mentionedly be doped in rare earth compound in the host glass take rare earth oxide as benchmark, balance to 100%, wherein, described rare earth compound one preferably comprises following component again:
CeO
2 0.1～2wt％
Sm
2O
3 0.1～2wt％。
Above-mentionedly be doped in rare earth compound in the host glass take rare earth oxide as benchmark, balance to 100%, wherein, another preferably comprises following component described rare earth compound:
CeO
2 0.1～2wt％
Sm
2O
3 0.1～2wt％
Eu
2O
3 0.1～2wt％
Tb
2O
3 0.1～2wt％
Dy
2O
3 0.1～2wt％。
Above-mentioned host glass is the iron content component also, with oxide compound Fe
2O
3Meter, iron level is lower than 150ppm.
Above-mentioned ultra-white photovoltaic glass thickness is preferably 3.2mm or 4mm, but this ultra-white photovoltaic glass thickness is not limited only to aforementioned thicknesses, can do suitable adjustment according to actual application environment.
Because above-mentioned ultra-white photovoltaic glass contains at least a ion among Rare-Earth Ce, Sm, Eu, Tb or the Dy, these rare earth ions itself not only do not absorb visible light, and effectively convert UV-light to visible light, thereby strengthened the transmitance of visible light, when this ultra-white photovoltaic glass is used for the glass cover-plate of solar cell, not only can improve the efficiency of conversion of battery, increase generated energy, but also can reduce UV-light wearing out to seal, sealing materials such as EVA.Meanwhile, this ultra-white photovoltaic glass adopts the host glass material of high-quality and reasonably fills a prescription, so that it has higher transmitance to visible light, and when this glass folding 3mm standard thickness, visible transmission ratio 〉=91.5%.
The present embodiment is selected above-mentioned Ce, Sm, Eu, Tb at last by great many of experiments and performance test, and one or more in five kinds of rare earth ions of Dy are doped in the host glass.And other rare earth ion not only can not be effectively produces absorption jump and fluorescent emission to UV-light, and can also absorb visible light and painted, affects the transmitance of visible light, so be not suitable for being applied to ultra-white photovoltaic glass.
Above-mentioned ultra-white photovoltaic glass preparation method, the method comprises the steps:
Host glass and the rare earth compound that is doped in the host glass are heated to 1500～1600 ℃ of fusings, after clarification and cooling, adopt floating process or calendering technology to make sheet glass, then obtain described ultra-white photovoltaic glass through annealing process.
Among this ultra-white photovoltaic glass preparation method, only need according to prescription each component to be mixed, and heat fused, need not special equipment and environmental requirement, its preparation method technique is simple; And obtain sheet glass with existing ripe floating process or calendering technology, so that the finished product productive rate is high; In addition, because rear-earth-doped ratio is less, do not affect existing floating process or calendering technology, only need carry out the small adjustment of processing parameter, therefore, the preparation method is easy to operate and control, and is suitable for suitability for industrialized production.
Below illustrate component different content of ultra-white photovoltaic glass of the present invention and preparation method thereof by a plurality of embodiment, with and the aspects such as application and performance.
Embodiment 1
Take oxide compound as benchmark, the SiO of ultra-white photovoltaic glass total weight percent 72wt% will be accounted for
2, 14wt% Na
2The Al of the CaO of O, 8wt%, the MgO of 4wt% and 1wt%
2O
3Host glass component and the rare earth compound Sm that accounts for ultra-white photovoltaic glass total weight percent 1.0wt%
2O
3Mix, this mixture heating up to 1550 ℃ is made its fusing again, then mixture that then will fusing adopts floating process or calendering technology to make sheet glass through clarification and cooling, at last sheet glass is obtained described ultra-white photovoltaic glass through annealing process.The utilizing emitted light spectrogram of the present embodiment ultra-white photovoltaic glass is seen Fig. 2, and its optimum transmit wavelength is 600nm, and the fluorescence intensity that produces is the strongest; The excitation light spectrogram of the present embodiment ultra-white photovoltaic glass is seen Fig. 3, and its maximum excitation wavelength is 400nm.When the thickness of the present embodiment ultra-white photovoltaic glass was 4mm, its transmittance curve that records was seen Fig. 1, and as known in the figure, its visible light transmissivity sees Table 1 up to 91.10%.
Embodiment 2
Take oxide compound as benchmark, the SiO of ultra-white photovoltaic glass total weight percent 72wt% will be accounted for
2, 14wt% Na
2The Al of the CaO of O, 8wt%, the MgO of 3wt% and 1wt%
2O
3Host glass component and the CeO that accounts for ultra-white photovoltaic glass total weight percent 1wt%
2Sm with 1wt%
2O
3Mix, this mixture heating up to 1550 ℃ is made its fusing again, then mixture that then will fusing adopts floating process or calendering technology to make sheet glass through clarification and cooling, at last sheet glass is obtained described ultra-white photovoltaic glass through annealing process.The utilizing emitted light spectrogram of the present embodiment ultra-white photovoltaic glass is seen Fig. 5, and its optimum transmit wavelength is 418nm, and the fluorescence intensity that produces is the strongest; Its excitation light spectrogram is seen Fig. 6, and its maximum excitation wavelength is 350nm.When the thickness of the present embodiment ultra-white photovoltaic glass was 4mm, its transmittance curve that records was seen Fig. 4, and as known in the figure, its visible light transmissivity sees Table 1 up to 90.62%.
Embodiment 3
Take oxide compound as benchmark, the SiO of ultra-white photovoltaic glass total weight percent 72wt% will be accounted for
2, 14wt% Na
2The Al of the CaO of O, 8wt%, the MgO of 3.5wt% and 0.5wt%
2O
3Host glass component and the rare earth compound Eu that accounts for ultra-white photovoltaic glass total weight percent 2.0wt%
2O
3Mix, this mixture heating up to 1560 ℃ is made its fusing again, then mixture that then will fusing adopts floating process or calendering technology to make sheet glass through clarification and cooling, at last sheet glass is obtained described ultra-white photovoltaic glass through annealing process.The utilizing emitted light spectrogram of the present embodiment ultra-white photovoltaic glass is seen Fig. 8, and its optimum transmit wavelength is 610nm, and the fluorescence intensity that produces is the strongest; The excitation light spectrogram of the present embodiment ultra-white photovoltaic glass is seen Fig. 9, and its maximum excitation wavelength is 390nm.When the thickness of the present embodiment ultra-white photovoltaic glass was 4mm, its transmittance curve that records was seen Fig. 7, and as known in the figure, its visible light transmissivity sees Table 1 up to 91.16%.
Embodiment 4
Take oxide compound as benchmark, the SiO of ultra-white photovoltaic glass total weight percent 72wt% will be accounted for
2, 14wt% Na
2The Al of the CaO of O, 8wt%, the MgO of 3.5wt% and 0.5wt%
2O
3Host glass component and the rare earth compound Tb that accounts for ultra-white photovoltaic glass total weight percent 2.0wt%
2O
3Mix, this mixture heating up to 1560 ℃ is made its fusing again, then mixture that then will fusing adopts floating process or calendering technology to make sheet glass through clarification and cooling, at last sheet glass is obtained described ultra-white photovoltaic glass through annealing process.The utilizing emitted light spectrogram of the present embodiment ultra-white photovoltaic glass is seen Figure 11, and among the figure, the optimum transmit wavelength is 541nm, and the fluorescence intensity that produces is the strongest; The excitation light spectrogram of the present embodiment ultra-white photovoltaic glass is seen Figure 12, and its maximum excitation wavelength is at 375nm.When the thickness of the present embodiment ultra-white photovoltaic glass was 4mm, its transmittance curve that records was seen Figure 10, and as known in the figure, its visible light transmissivity sees Table 1 up to 91.20%.
Embodiment 5
Take oxide compound as benchmark, the SiO of ultra-white photovoltaic glass total weight percent 72wt% will be accounted for
2, 14wt% Na
2The Al of the CaO of O, 8wt%, the MgO of 3.5wt% and 0.5wt%
2O
3Host glass component and the rare earth compound Dy that accounts for ultra-white photovoltaic glass total weight percent 2.0wt%
2O
3Mix, this mixture heating up to 1560 ℃ is made its fusing again, then mixture that then will fusing adopts floating process or calendering technology to make sheet glass through clarification and cooling, at last sheet glass is obtained described ultra-white photovoltaic glass through annealing process.The utilizing emitted light spectrogram of the present embodiment ultra-white photovoltaic glass is seen Figure 14, and among the figure, the optimum transmit wavelength is 574nm, and the fluorescence intensity that produces is the strongest; The excitation light spectrogram of the present embodiment ultra-white photovoltaic glass is seen Figure 15, and its maximum excitation wavelength is at 350nm.When the thickness of the present embodiment ultra-white photovoltaic glass was 4mm, its transmittance curve that records was seen Figure 13, and as known in the figure, its visible light transmissivity sees Table 1 up to 91.13%.
The visible light transmissivity of the prepared ultra-white photovoltaic glass of table 1 embodiment
The above only is preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. ultra-white photovoltaic glass is characterized in that: comprise host glass and be doped in rare earth compound in the host glass, described rare earth compound is rare earth oxide or ores containing rare earths thing, and described rare earth oxide is Sm
2O
3, Eu
2O
3, Tb
2O
3, Dy
2O
3In wherein a kind of or CeO
2With any the combination among them, described ores containing rare earths thing be contain Sm, Eu, Tb, Dy wherein a kind of element rare-earth mineral or for containing the rare-earth mineral of Ce and any element among them.
2. ultra-white photovoltaic glass as claimed in claim 1, it is characterized in that: described host glass is take oxide compound as benchmark, and its component that comprises is:
Describedly be doped in rare earth compound in the host glass take rare earth oxide as benchmark, balance to 100%.
3. ultra-white photovoltaic glass as claimed in claim 1, it is characterized in that: described host glass comprises following component take oxide compound as benchmark:
Describedly be doped in rare earth compound in the host glass take rare earth oxide as benchmark, balance to 100%, wherein, described rare earth compound comprises following component:
CeO
20.1～2wt％
Sm
2O
30.1～2wt％。
4. ultra-white photovoltaic glass as claimed in claim 2 is characterized in that: also contain Fe in the described host glass, with oxide compound Fe
2O
3Meter, iron level is lower than 150ppm.
5. ultra-white photovoltaic glass as claimed in claim 1, it is characterized in that: this ultra-white photovoltaic glass thickness is 3.2mm or 4mm.
6. ultra-white photovoltaic glass preparation method, the method comprises the steps:
Host glass and the rare earth compound that is doped in the host glass are heated to 1500～1600 ℃ of fusings, after clarification and cooling, adopt floating process or calendering technology to make sheet glass, then obtain described ultra-white photovoltaic glass through annealing process, described rare earth compound is rare earth oxide or ores containing rare earths thing, and described rare earth oxide is Sm
2O
3, Eu
2O
3, Tb
2O
3, Dy
2O
3In wherein a kind of or CeO
2With any the combination among them, described ores containing rare earths thing be Sm, Eu, Tb, Dy wherein a kind of element rare-earth mineral or for containing the rare-earth mineral of Ce and any element among them.
7. ultra-white photovoltaic glass as claimed in claim 6, it is characterized in that: described host glass is take oxide compound as benchmark, and its component that comprises is:
Describedly be doped in rare earth compound in the host glass take rare earth oxide as benchmark, balance to 100%, described rare earth compound content is 0.1～2wt%.
8. the application of ultra-white photovoltaic glass according to claim 1 in the solar battery glass cover plate.
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| CN101066835A (en) * | 2007-06-11 | 2007-11-07 | 中国洛阳浮法玻璃集团有限责任公司 | Solar energy very white rolled glass components |
| CN101081724A (en) * | 2007-06-15 | 2007-12-05 | 上海福莱特玻璃有限公司 | Ultraviolet blocking-up solar energy ultra-white configurated glass and method for manufacturing the same |
| CN101624262A (en) * | 2009-07-29 | 2010-01-13 | 内蒙古科技大学 | Colorless and transparent functional glass with strong ultraviolet absorption capability |
| CN102092941A (en) * | 2010-12-02 | 2011-06-15 | 内蒙古科技大学 | Ultra-white glass |
-
2010
- 2010-05-27 CN CN 201010190100 patent/CN102260041B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1753842A (en) * | 2003-04-01 | 2006-03-29 | 日本电气硝子株式会社 | Luminescent glass article and method of manufacturing the same |
| CN101066835A (en) * | 2007-06-11 | 2007-11-07 | 中国洛阳浮法玻璃集团有限责任公司 | Solar energy very white rolled glass components |
| CN101081724A (en) * | 2007-06-15 | 2007-12-05 | 上海福莱特玻璃有限公司 | Ultraviolet blocking-up solar energy ultra-white configurated glass and method for manufacturing the same |
| CN101624262A (en) * | 2009-07-29 | 2010-01-13 | 内蒙古科技大学 | Colorless and transparent functional glass with strong ultraviolet absorption capability |
| CN102092941A (en) * | 2010-12-02 | 2011-06-15 | 内蒙古科技大学 | Ultra-white glass |
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| CN102260041A (en) | 2011-11-30 |
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