WO2013008186A2 - Luminescent solar energy concentrator - Google Patents

Luminescent solar energy concentrator Download PDF

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Publication number
WO2013008186A2
WO2013008186A2 PCT/IB2012/053537 IB2012053537W WO2013008186A2 WO 2013008186 A2 WO2013008186 A2 WO 2013008186A2 IB 2012053537 W IB2012053537 W IB 2012053537W WO 2013008186 A2 WO2013008186 A2 WO 2013008186A2
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WO
WIPO (PCT)
Prior art keywords
inorganic
luminescent material
solar energy
energy concentrator
refractive index
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PCT/IB2012/053537
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French (fr)
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WO2013008186A3 (en
Inventor
Dirk Kornelis Gerhardus De Boer
Marcus Antonius Verschuuren
Remco VAN BRAKEL
Wouter Dekkers
Original Assignee
Koninklijke Philips Electronics N.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
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Application filed by Koninklijke Philips Electronics N.V. filed Critical Koninklijke Philips Electronics N.V.
Publication of WO2013008186A2 publication Critical patent/WO2013008186A2/en
Publication of WO2013008186A3 publication Critical patent/WO2013008186A3/en

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    • 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

Definitions

  • the present invention is directed to converter materials for solar cells.
  • Luminescent solar energy concentrators are devices to decrease the costs of solar cells and have recently been introduced in the art e.g. in the WO 2010/67296, hereby incorporated by reference.
  • a luminescent solar energy concentrator for a photovoltaic cell comprising a waveguide comprising a transparent matrix having (i) particles of an inorganic luminescent material dispersed therein and/or (ii) an inorganic luminescent material provided at at least one side thereof, wherein the waveguide is associated with the photovoltaic cell so that, in use, at least some of the light emitted from the luminescent material passes into the photovoltaic cell to generate a voltage in the cell, whereby the difference of the refractive index 3 ⁇ 4 of the inorganic luminescent material and the refractive index n 2 of the transparent matrix, both measured at the emission peak of the inorganic luminescent material is ⁇ 0.6.
  • the efficiency of the concentrator is increased due to less light emitted by the inorganic luminescent material leaving the concentrator without passing into the photovoltaic cell
  • emission peak in the sense of the present invention especially means and/or includes the wavelength between 500 nm and 1000 nm where the emission of the inorganic luminescent material has the highest intensity
  • the difference of the refractive index 3 ⁇ 4 of the inorganic luminescent material and the refractive index n 2 of the transparent matrix, both measured at the emission peak of the inorganic luminescent material is ⁇ 0.4, more preferred ⁇ 0.2, yet more preferred ⁇ 0.13 and most preferred ⁇ 0.08.
  • the difference of the refractive index 3 ⁇ 4 of the inorganic luminescent material and the refractive index n 2 of the transparent matrix, both measured at the absorption peak of the inorganic luminescent material is >0.02, more preferred >0.03, most preferred >0.05. It has been shown in practice for many applications that this slight difference in refractive index may be advantageous since the resulting scattering of the incident radiation has the effect of increasing the path length in the phosphor and hence enhancing the chance of absorption.
  • absorption peak in the sense of the present invention especially means and/or includes the wavelength between 280 nm and 600 nm where the absorption of the inorganic luminescent material has the highest intensity.
  • the inorganic luminescent material comprises at least one ion selected from rare-earth ions like Sm 2+ , Ce 3+ , Eu 3+ , Eu 2+ , Er 3+ , Nd 3+ , Ho 3+ , Yb 3+ ,Tm 3+ , Sm 3+ , Dy 3+ ' Mn 2+ or Yb 2+ .
  • rare-earth ions like Sm 2+ , Ce 3+ , Eu 3+ , Eu 2+ , Er 3+ , Nd 3+ , Ho 3+ , Yb 3+ ,Tm 3+ , Sm 3+ , Dy 3+ ' Mn 2+ or Yb 2+ .
  • the inorganic luminescent material is selected from the group comprising oxidic, nitridic, oxidonitridic, fluoridic, borate, phosphate materials and mixtures thereof. These materials have been found advantageous in practice. Additionally or alternatively according to another embodiment of the present invention, the converter material is selected from the group comprising alkaline and/or earth alkaline containing materials.
  • the inorganic luminescent material is selected from the group comprising EAi_ x B 4 0v:Sm x with EA being an earth alkaline metal or mixtures of earth alkaline metals, Gd3Ga 5 0i 2 :Ce,Cr, CaAlSiN3:Ce,Eu or mixtures thereof.
  • the average diameter of the particles is >50 nm and ⁇ 10 ⁇ , preferably >100 nm and ⁇ 5 ⁇ and most preferred >300 nm and ⁇ 1 ⁇ m. This size has been shown to be a good compromise to ensure scattering (which will not happen at very small sizes) and a good processability of the particles.
  • the transparent matrix material is selected from the group comprising:
  • especially high-index organic polyimides are especially preferred.
  • examples of such polyimides are e.g. the material OptiNDEXTM Dl polyimide, sold by the company Brewer, Rolla, MO, USA.
  • Another class of high- index organic polymers is that of episulfides (e.g. those developed by Mitsubishi Gas Company).
  • Suitable polymers are PVP, PVB, Poly(meth)acrylates, Polycarbonates and/or polyimides which may have inorganic particles like oxides, especially Ti0 2 , Hf0 2 , Zr0 2 , BaTiC"3, SrTiC"3 dispersed therein.
  • the average size of these particles is ⁇ 100 nm, more preferred ⁇ 70 nm and most preferred ⁇ 30 nm.
  • the fraction of particles having a particle size of >200nm is ⁇ 5 (wt%), more preferred ⁇ 3 (wt%) and most preferred ⁇ 2 (wt%).
  • Suitable materials are silicone polymers such as PDMS (Polydimethylsiloxane) or silicone resins like the resin "SILRES", sold by the Wacker Company, Burghausen, Germany.
  • silicone polymers such as PDMS (Polydimethylsiloxane) or silicone resins like the resin "SILRES", sold by the Wacker Company, Burghausen, Germany.
  • the average size of these particles is ⁇ 100 nm, more preferred ⁇ 70 nm and most preferred ⁇ 30 nm.
  • the fraction of particles having a particle size of >200nm is ⁇ 5 (wt%), more preferred ⁇ 3 (wt%) and most preferred ⁇ 2 (wt%).
  • Suitable materials are especially inorganic oxides like Ti0 2 , Hf0 2 , Zr0 2 , BaTi0 3 , SrTi0 3 or mixtures of these materials. These materials may be incorporated in sol- gel (silicate-based) material.
  • sol-gel materials may be easily processed, whereas the refractive index may be tuned by adding an appropriate amount of the mentioned high-index oxide material to the low-index (approx. 1.4) silicate.
  • Fig. 1 shows a very schematic cross-sectional view through a luminescent solar energy concentrator and a solar cell according to a first embodiment of the present invention.
  • Fig. 2 shows the embodiment of Fig. 1 explaning the path of light
  • Fig. 3 shows a more detailled view through the embodiment of Figs 1 and 2.
  • Fig. 4 shows a comparative example in the same view as Fig. 3
  • Fig. 5 shows a diagram showing the influence of nanoparticles on the
  • Fig. 1 shows a very schematic cross-sectional view through a luminescent solar energy concentrator 1 and a solar cell 4 according to a first embodiment of the present invention.
  • the luminescent solar energy concentrator 1 comprises a light guide 3 and a transparent matrix 2 having inorganic luminescent particles dispersed therein (not shown in Fig. 1, cf. Fig. 3).
  • Fig. 2 shows the embodiment of Fig. 1 explaning the path of light and the functioning of the luminescent solar energy concentrator: A part of the solar light that incidents through the transparent matrix into one of the inorganic luminescent particles (indicated by the dashed line) is converted by said particle to light of a different wavelight, which eventually passes into the solar cell 4.
  • Fig. 3 shows a more detailled view through the embodiment of Figs 1 and 2 and shows the inorganic luminescent particles 5 which are dispersed in the transparent matrix 2.
  • the particles 5 and the matrix 2 are index- matched, the light emitted from the particles 5 will not leave the matrix 2 or the light guide 3, whereas in case that the both are not index-matched (as in Fig. 4 which shows a comparative example), some of the light will leave the luminescent solar energy concentrator 1, thereby causing efficiency losses.
  • Fig. 5 shows a diagram showing the influence of nanoparticles (here: Ti0 2 ) on the refractive index in an organic binder (here: PVB) having nanoparticles dispersed therein.
  • Ti0 2 dispersion with an average particle size of about 60nm (Titandioxid P25, Degussa) in ethanol (35% m/m) was added to a PVB solution.
  • the mixture is then mixed with a speedmixer (2000-2500 rpm for 2 minutes) the mixture was blade coated with a ⁇ blade and dried at room temperature.
  • the ratio Ti0 2 /PVB-binder was varied to create a calibration curve
  • Fig. 5 it is possible to increase the refractive index by nearly 0.3, thereby allowing to fit refractive index of the transparent matrix (which is formed by the organic binder and the nanoparticular Ti0 2 ) to that of the inorganic luminescent particles.
  • the refractive index of SrB 4 C"7 is shown as a dashed line.

Abstract

The invention relates to an Luminescent solar energy concentrator where the matrix material and the inorganic luminescent compounds which are dispersed therein or associated therewith are index-matched.

Description

LUMINESCENT SOLAR ENERGY CONCENTRATOR
FIELD OF THE INVENTION
The present invention is directed to converter materials for solar cells.
BACKGROUND OF THE INVENTION
Luminescent solar energy concentrators (LSC) are devices to decrease the costs of solar cells and have recently been introduced in the art e.g. in the WO 2010/67296, hereby incorporated by reference.
Due to the recency of the developments of LSCs there is the constant need for improvement.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide an improved luminescent solar energy concentrator.
This object is solved by a luminescent solar energy concentrator according to claim 1 of the present invention. Accordingly, a luminescent solar energy concentrator for a photovoltaic cell is provided comprising a waveguide comprising a transparent matrix having (i) particles of an inorganic luminescent material dispersed therein and/or (ii) an inorganic luminescent material provided at at least one side thereof, wherein the waveguide is associated with the photovoltaic cell so that, in use, at least some of the light emitted from the luminescent material passes into the photovoltaic cell to generate a voltage in the cell, whereby the difference of the refractive index ¾ of the inorganic luminescent material and the refractive index n2 of the transparent matrix, both measured at the emission peak of the inorganic luminescent material is <0.6.
Surprisingly it has been found that such a luminescent solar energy
concentrator has for a wide range of applications within the present invention at least one of the following advantages:
The efficiency of the concentrator is increased due to less light emitted by the inorganic luminescent material leaving the concentrator without passing into the photovoltaic cell
If the light is not scattered, there is less chance on reabsorption. For some applications, it looks nicer to have a transparent, non-scattering material.
The term "emission peak" in the sense of the present invention especially means and/or includes the wavelength between 500 nm and 1000 nm where the emission of the inorganic luminescent material has the highest intensity
According to a preferred embodiment, the difference of the refractive index ¾ of the inorganic luminescent material and the refractive index n2 of the transparent matrix, both measured at the emission peak of the inorganic luminescent material is <0.4, more preferred <0.2, yet more preferred <0.13 and most preferred <0.08.
According to a preferred embodiment, the difference of the refractive index ¾ of the inorganic luminescent material and the refractive index n2 of the transparent matrix, both measured at the absorption peak of the inorganic luminescent material is >0.02, more preferred >0.03, most preferred >0.05. It has been shown in practice for many applications that this slight difference in refractive index may be advantageous since the resulting scattering of the incident radiation has the effect of increasing the path length in the phosphor and hence enhancing the chance of absorption.
The term "absorption peak" in the sense of the present invention especially means and/or includes the wavelength between 280 nm and 600 nm where the absorption of the inorganic luminescent material has the highest intensity.
According to a preferred embodiment of the invention, the inorganic luminescent material comprises at least one ion selected from rare-earth ions like Sm2+, Ce3+, Eu3+, Eu2+, Er3+, Nd3+, Ho3+, Yb3+,Tm3+, Sm3+, Dy3+' Mn2+ or Yb2+. These materials have proven themselves in practice.
Preferably the inorganic luminescent material is selected from the group comprising oxidic, nitridic, oxidonitridic, fluoridic, borate, phosphate materials and mixtures thereof. These materials have been found advantageous in practice. Additionally or alternatively according to another embodiment of the present invention, the converter material is selected from the group comprising alkaline and/or earth alkaline containing materials.
Preferably the inorganic luminescent material is selected from the group comprising EAi_xB40v:Smx with EA being an earth alkaline metal or mixtures of earth alkaline metals, Gd3Ga50i2:Ce,Cr, CaAlSiN3:Ce,Eu or mixtures thereof.
According to a preferred embodiment of the present invention, in case the inorganic luminescent material is provided in particle form, the average diameter of the particles is >50 nm and <10 μηι, preferably >100 nm and <5 μηι and most preferred >300 nm and <1 μm. This size has been shown to be a good compromise to ensure scattering (which will not happen at very small sizes) and a good processability of the particles.
Preferably the the transparent matrix material is selected from the group comprising:
a) high- index organic polymers
b) organic polymers having inorganic particles dispersed therein c) silicone polymers and/or resins
d) inorganic matrix materials
or mixtures thereof. These materials are in the following described in more detail, however it should be noted that this is for further understanding of the invention only and is not intended to be limiting or to be understood in a way that the present invention is intended to include only the materials described hereforth.
Group a): high- index organic polymers
In this Group, especially high-index organic polyimides are especially preferred. Examples of such polyimides are e.g. the material OptiNDEX™ Dl polyimide, sold by the company Brewer, Rolla, MO, USA.
Another class of high- index organic polymers is that of episulfides (e.g. those developed by Mitsubishi Gas Company).
Group b): organic polymers having inorganic particles dispersed therein
In order to match the refractive index of the matrix material and the inorganic luminescent material the inventors have found out that it is possible to use organic polymers which initially have a lower refractive index than required and to mix them with inorganic particles.
Suitable polymers are PVP, PVB, Poly(meth)acrylates, Polycarbonates and/or polyimides which may have inorganic particles like oxides, especially Ti02, Hf02, Zr02, BaTiC"3, SrTiC"3 dispersed therein.
In case inorganic particls are used it is especially preferred that the average size of these particles is <100 nm, more preferred <70 nm and most preferred <30 nm.
Alternatively and/or additionally it is preferred that the fraction of particles having a particle size of >200nm is <5 (wt%), more preferred <3 (wt%) and most preferred <2 (wt%).
Group c): silicone polymers and/or resins
Suitable materials are silicone polymers such as PDMS (Polydimethylsiloxane) or silicone resins like the resin "SILRES", sold by the Wacker Company, Burghausen, Germany. In order to match the refractive index of the matrix material and the inorganic luminescent material the inventors have found out that it is possible to use silicone polymers which initially have a lower refractive index than required and to mix them with inorganic particles.
In case inorganic particls are used it is especially preferred that the average size of these particles is <100 nm, more preferred <70 nm and most preferred <30 nm. Alternatively and/or additionally it is preferred that the fraction of particles having a particle size of >200nm is <5 (wt%), more preferred <3 (wt%) and most preferred <2 (wt%).
Group d): inorganic matrix materials
Suitable materials are especially inorganic oxides like Ti02, Hf02, Zr02, BaTi03, SrTi03 or mixtures of these materials. These materials may be incorporated in sol- gel (silicate-based) material. The sol-gel materials may be easily processed, whereas the refractive index may be tuned by adding an appropriate amount of the mentioned high-index oxide material to the low-index (approx. 1.4) silicate.
The aforementioned components, as well as the claimed components and the components to be used in accordance with the invention in the described embodiments, are not subject to any special exceptions with respect to their size, shape, material selection and technical concept such that the selection criteria known in the pertinent field can be applied without limitations.
BRIEF DESCRIPTION OF THE DRAWINGS
Additional details, features, characteristics and advantages of the object of the invention are disclosed in the subclaims, the figures and the following description of the respective figures and examples, which— in an exemplary fashion— show several embodiments and examples of Luminescent solar energy concentrators according to the invention.
Fig. 1 shows a very schematic cross-sectional view through a luminescent solar energy concentrator and a solar cell according to a first embodiment of the present invention.
Fig. 2 shows the embodiment of Fig. 1 explaning the path of light
Fig. 3 shows a more detailled view through the embodiment of Figs 1 and 2.
Fig. 4 shows a comparative example in the same view as Fig. 3 Fig. 5 shows a diagram showing the influence of nanoparticles on the
refractive index in an organic binder having nanoparticles dispersed therein.
Fig. 1 shows a very schematic cross-sectional view through a luminescent solar energy concentrator 1 and a solar cell 4 according to a first embodiment of the present invention. The luminescent solar energy concentrator 1 comprises a light guide 3 and a transparent matrix 2 having inorganic luminescent particles dispersed therein (not shown in Fig. 1, cf. Fig. 3).
Fig. 2 shows the embodiment of Fig. 1 explaning the path of light and the functioning of the luminescent solar energy concentrator: A part of the solar light that incidents through the transparent matrix into one of the inorganic luminescent particles (indicated by the dashed line) is converted by said particle to light of a different wavelight, which eventually passes into the solar cell 4.
Fig. 3 shows a more detailled view through the embodiment of Figs 1 and 2 and shows the inorganic luminescent particles 5 which are dispersed in the transparent matrix 2. As can be seen from Fig. 3, due to the fact that the particles 5 and the matrix 2 are index- matched, the light emitted from the particles 5 will not leave the matrix 2 or the light guide 3, whereas in case that the both are not index-matched (as in Fig. 4 which shows a comparative example), some of the light will leave the luminescent solar energy concentrator 1, thereby causing efficiency losses.
Fig. 5 shows a diagram showing the influence of nanoparticles (here: Ti02) on the refractive index in an organic binder (here: PVB) having nanoparticles dispersed therein.
To this end, Ti02 dispersion with an average particle size of about 60nm (Titandioxid P25, Degussa) in ethanol (35% m/m) was added to a PVB solution. The mixture is then mixed with a speedmixer (2000-2500 rpm for 2 minutes) the mixture was blade coated with a ΙΟΟμιη blade and dried at room temperature. The ratio Ti02/PVB-binder was varied to create a calibration curve
As can be seen in Fig. 5 it is possible to increase the refractive index by nearly 0.3, thereby allowing to fit refractive index of the transparent matrix (which is formed by the organic binder and the nanoparticular Ti02) to that of the inorganic luminescent particles. As an example, the refractive index of SrB4C"7 is shown as a dashed line.
The particular combinations of elements and features in the above detailed embodiments are exemplary only; the interchanging and substitution of these teachings with other teachings in this and the patents/applications incorporated by reference are also expressly contemplated. As those skilled in the art will recognize, variations, modifications, and other implementations of what is described herein can occur to those of ordinary skill in the art without departing from the spirit and the scope of the invention as claimed.
Accordingly, the foregoing description is by way of example only and is not intended as limiting. In the claims, the word "comprising" does not exclude other elements or steps, and the indefinite article "a" or "an" does not exclude a plurality. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measured cannot be used to advantage. The invention's scope is defined in the following claims and the equivalents thereto. Furthermore, reference signs used in the description and claims do not limit the scope of the invention as claimed.

Claims

CLAIMS:
1. Luminescent solar energy concentrator for a photovoltaic cell comprising a waveguide comprising a transparent matrix having (i) particles of an inorganic luminescent material dispersed therein and/or (ii) an inorganic luminescent material provided at at least one side thereof, wherein the waveguide is associated with the photovoltaic cell so that, in use, at least some of the light emitted from the luminescent material passes into the photovoltaic cell to generate a voltage in the cell, whereby
the difference of the refractive index ¾ of the inorganic luminescent material and the refractive index n2 of the transparent matrix, both measured at the emission peak of the inorganic luminescent material is <0.6
2. The luminescent solar energy concentrator of Claim 1, whereby the difference of the refractive index ¾ of the inorganic luminescent material and the refractive index n2 of the transparent matrix, both measured at the emission peak of the inorganic luminescent material is <0.4
3. The luminescent solar energy concentrator of Claim 1 or 2, whereby the difference of the refractive index ¾ of the inorganic luminescent material and the refractive index n2 of the transparent matrix, both measured at the absorption peak of the inorganic luminescent material is >0.02.
4. The Luminescent solar energy concentrator of any of the Claims 1 to 3, whereby the inorganic luminescent material comprises at least one ion selected from Sm2+, Ce3+, Eu2+ or Yb2+.
5. The Luminescent solar energy concentrator of any of the Claims 1 to 4 whereby the transparent matrix material is selected from the group comprising
a) high- index organic polymers
b) organic polymers having inorganic particles dispersed therein c) silicone polymers and/or resins d) inorganic matrix materials
and/or mixtures thereof
6. The Luminescent solar energy concentrator of any of the Claims 1 to 5, whereby the inorganic luminescent material is selected from the group comprising oxidic, nitridic, oxidonitridic, fluoridic, borate, phosphate materials and mixtures thereof.
7. The Luminescent solar energy concentrator of any of the Claims 1 to 6, whereby the inorganic luminescent material is provided in particle form and the average diameter of the particles is >50 nm and <10 μιη.
8. The Luminescent solar energy concentrator of any of the Claims 1 to 7, whereby the inorganic luminescent material is provided in particle form and the average diameter of the particles is > 100 nm and <5 μιη.
PCT/IB2012/053537 2011-07-12 2012-07-11 Luminescent solar energy concentrator WO2013008186A2 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11251323B2 (en) 2016-07-12 2022-02-15 Rensselaer Polytechnic Institute Solar power harvesting building envelope

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