Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
  • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
  • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass

Definitions

• the present invention relates to an improved glass plate for a solar unit, and more especially to a glass composition for the plate.
• This composition exhibits high transmission across the wavelength range over which the solar material (e.g. photovoltaic material) comprised in such a unit is operational.
• solar unit means any and/or all of the following: an individual photovoltaic cell (also known in the art as a solar cell), a module comprising multiple photovoltaic cells, a solar mirror, a solar lens and a solar thermal system.
• a solar mirror is a mirror which reflects and/or focuses electromagnetic radiation from the sun (e.g. infrared (IR), visible and/or ultraviolet (UV) radiation) onto a device that is capable of collecting and/or generating energy, such as heat or electricity. Such a mirror may also be known as a concentrator.
• a solar thermal system may comprise an array of heat-absorbing fluid- filled tubes, or an equivalent solar heating system, protected by a glass cover plate.
• a photovoltaic solar unit typically comprises a glass cover plate, through which solar electromagnetic radiation passes to one or more underlying layers of solar material, which in this context means material which produces electricity under the influence of visible light, IR and UV radiation, (commonly known as photovoltaic material).
• a backing plate or substrate, which may also be made of glass, is usually included to provide mechanical stability to the unit.
• a solar unit in the form of a mirror typically comprises a highly transmitting glass substrate having a layer of a reflective metal such as silver on its rear or second surface (i.e. the surface which is further from the sun, compared with the surface on which light is incident).
• a reflective metal such as silver on its rear or second surface
• solar material means the heat-absorbing fluid- filled tube array or equivalent.
• Crystalline photovoltaic materials include gallium arsenide (GaAs) and other Group III - V semiconductor material systems, and both single crystal silicon (c-Si) and polycrystalline silicon (mc-Si). These materials are used in the form of thin, brittle wafers and thus require protection against deflection and breakage, usually by the presence of a cover plate.
• GaAs gallium arsenide
• c-Si single crystal silicon
• mc-Si polycrystalline silicon
• Thin film coating materials include, but are not limited to, copper indium diselenide (CIS), copper indium gallium diselenide (CIGS), cadmium telluride (CdTe) and amorphous silicon (a-Si). Use of these materials also requires the presence of a cover plate; the cover plate may also be the substrate for growth of the coating. With the thin film type, glass may act as the substrate for growth of the photovoltaic layers. Organic materials include dye-sensitized cells.
• Watt peak is the number of watts output when a photovoltaic unit is illuminated with solar radiation corresponding to Air Mass 1.5 at 1000 watts per square metre intensity at 25 0 C ambient temperature.
• DSHT Direct Solar Heat Transmission
• TE Transmitted Energy
• DSHT is an integrated transmission value over the wavelength range 300-2500 nm, which encompasses the spectral response ranges of all of the photovoltaic materials described earlier.
• the cover plate of a photovoltaic unit may incorporate one or more external anti-reflective layers or a three-dimensional pattern to increase the intensity of transmitted radiation compared to a standard pane of glass having neither of these features. Use of one of more external anti-reflective layers is also useful for increasing transmission of IR, UV and visible light in a mirror solar unit.
• the cover glass itself should show no absorption over the wavelength region which is utilised by the photovoltaic material, or reflected by the solar mirror, or absorbed by the solar thermal system. In practice this is not possible due to the presence of trace impurities present in even the purest raw glass-making materials. These impurities include iron, cobalt, etc., which occur naturally in the minerals and processed materials used to make glass.
• the principal colourant of concern is iron and particularly when it is present in the ferrous Fe(II) state.
• An Fe 2+ ion gives glass a blue-green colouration, which results from an absorption band with a maximum absorption (i.e. minimum transmission) around 1050 nm, known as the ferrous absorption band.
• An alternative, or additional, approach to the selective purchasing of raw materials is to ensure that as much as feasible of the iron present in the glass is in the oxidised, less strongly absorbing, ferric Fe(III) state, i.e. the amount of iron in the ferrous Fe(II) state is reduced, or at the very least kept constant if other conditions/ingredients are varied.
• This may be done by providing the necessary oxidising conditions in a glass-making furnace, however this can be difficult to control and/or the desired oxidation state may not be achieved.
• this may be done by addition of one or more oxidising agents, e.g.
• antimony oxide cannot be used in the float process as antimony forms an undesirable alloy with the molten tin present in the float bath.
• a further means of improving transmission of radiation is through simple application of the Beer-Lambert law: the thinner a piece of glass of a chosen composition is made, the lower its absorption will be.
• a 4 mm thick piece of glass containing 0.1 % by weight of iron 25 % of it being in the ferrous state
• a 2 mm thick piece of the 0.1 % weight iron glass would show half the absorption of its 4 mm thick parent.
• US patent application US2008/0085827A1 discloses a glass having a high light transmission and neutral colour.
• the glass includes a low amount of iron coupled with zinc oxide and/or erbium oxide in amounts designed to provide a neutral colour.
• pure or low-iron raw materials are expensive, and this restricts their use in large-scale commercial operations.
• erbium oxide is also expensive.
• the present invention provides a solar unit glass plate having a composition comprising the following constituents, the amounts of which are expressed as percentages by weight:
• total iron is expressed as if all iron present were present as ferric oxide (Fe 2 O 3 ), as is known in the art.
• the ferrous level is determined optically using molecular absorption spectrophotometry.
• Glass of such a composition is effective at increasing (and potentially maximising) the efficiency of a solar unit of which it may form a part because of the increased (and potentially maximised) degree of radiation transmitted by it.
• DSHT is not the most effective way to discriminate between glass cover plates for photovoltaic solar units because the DSHT wavelength range is far wider than that utilised by conventional photovoltaic materials, by which it is meant materials that currently collectively operate over the range 400-1100 nm.
• a high or low transmission outside this "active" region is of secondary importance to a comparison of different glass cover plates.
• two different cover glass plates could have the same transmission over the active wavelength range and be used to produce otherwise identical photovoltaic solar units having the same cell efficiency despite having different DSHT values.
• a glass plate A has a high transmission across the full DSHT range (300-2500 nm), whereas a glass plate B, because it has absorption peaks in the 300-400 nm and 1100-2500 nm ranges, has an overall lower DSHT.
• both glass plate A and glass plate B give the same cell efficiencies by virtue of them having the same transmission in the active wavelength range (400-1100 nm).
• glass plate C and glass plate D may have the same DSHT values but give different cell efficiencies because one has an absorption band within the 400-1100 nm range whilst the other has equivalent absorption bands outside this wavelength range. For this reason it is believed to be more appropriate to describe photovoltaic solar unit (cover) glass plates using the 400-1100 nm definition of transmission, as is becoming standard in the solar energy industry.
• the invention also provides a glass plate for a solar unit, the plate having a composition comprising the following constituents, the amounts of which are expressed as percentages by weight:
• the glass plate may be flat (within the meaning of "flat” in general use in the flat glass industry) or curved; any curvature is the result of applying a shaping process to flat glass.
• the amount of SrO present in the composition may be between 3 and 8 %, preferably between 4 and 6 %.
• the amount of BaO present in the composition may be between 2 and 8 %, preferably between 3 and 6%.
• strontia and baria will be added to glass-making ingredients as carbonates, both of which are substantially iron- free raw materials, thus contributing to achievement of a low- iron glass.
• MgO affects the wavelength at which ferrous iron absorbs
• it is preferably present in the composition in an amount less than or equal to 1 %, preferably less than or equal to 0.4 % and most preferably in as small an amount as possible (less than 0.2 %).
• magnesia may be completely absent from the glass composition (not least because the raw material used to incorporate magnesia in a glass composition, dolomite, is difficult to obtain in a low-iron or iron-free form). However in practice this may not be possible, e.g. because of the necessity for reasonably quick transition times from magnesia-containing glass compositions (which may contain up to around 4.5 % MgO).
• a compromise may be reached by inclusion of magnesia at levels of 0.1 to 0.2 %, or 0.2 to 0.4 %. It appears that reduction of MgO to these low levels, along with the other changes to the glass composition compared to a standard clear glass, contributes to movement of the ferrous absorption band described earlier.
• Na 2 O (soda) may advantageously be present in an amount less than 16 %, preferably less than 15 % (around 14 % being preferred).
• Soda is a fluxing agent which is used to promote melting reactions between the batch ingredients, and so is an essential glass-making ingredient.
• the summed amount of the alkaline earth metal oxide constituents in the composition is in the range 10 - 20 %, preferably 11 - 18%, most preferably 12 - 18%.
• any of the glass compositions described above may be prepared using one or more of the following oxidising agents: nitrates of sodium and potassium and oxides of antimony, arsenic, cerium, manganese, vanadium, copper and titanium.
• oxidising agents nitrates of sodium and potassium and oxides of antimony, arsenic, cerium, manganese, vanadium, copper and titanium.
• Such materials may be included in the glass composition to promote oxidation of ferrous Fe(II) iron to ferric Fe(III) iron, and so to reduce the intensity of the ferrous absorption band especially in the spectral response region of photovoltaic materials (i.e. the active wavelength range).
• the glass may be free of any or all of ZnO, Li 2 O, B2O3, Er 2 O 3 or Sb 2 O 3 . Some of these materials are expensive, others are incompatible with certain manufacturing processes.
• the amount of iron present in the glass in the ferrous Fe(II) state is less than 40 %, preferably less than 30 or 25 %, most preferably between 15 and 22 %.
• these measures may result in the maximum of the absorption band due to iron in the ferrous Fe(II) state being positioned between 1120 and 1500 nm, preferably between 1125 and 1400 nm, and most preferably between 1130 and 1300 nm.
• the cover glass plate may additionally be tinted for aesthetic effect, by incorporation of colourants in the glass-making ingredients.
• tinting ingredients may reduce the efficiency of the unit, i.e. reduce the efficiency of photovoltaic conversion in BIPVs. This reduction may be mitigated by further alteration and optimisation of the base glass composition, as described herein, however for maximum cell efficiency, the cover glass plate should be as clear as possible.
• the glass may be formed by any of the known flat glass forming processes, including in particular the float process and the rolled processes, especially the variant employing twin water-cooled rollers.
• a glass plate according to the invention may conveniently be provided in annealed, sheet form.
• a sheet of glass may be provided in a thickness between 0.5 and 10 mm, preferably between 1 and 5 mm, to balance the mechanical stability afforded with acceptable weight.
• Said sheets may then be cut to the desired size and further processed as required. Such further processing may involve toughening or semi-toughening of the glass to impart desired impact resistance characteristics.
• Standard clear glass has ⁇ of approximately 90 x 10 ⁇ 7 0 C "1 between 50 and 350 0 C, whereas glass according to the invention may have ⁇ greater than 100 x 10 "7 0 C "1 between 50 and 350 0 C, preferably around 102 x 10 "7 0 C 1 between 50 and 350 0 C. It is believed that the higher the content of soda in a glass composition, the higher the coefficient of thermal expansion of the glass, and the more easily the glass may be toughened. Beneficial toughening characteristics may lead to further production advantages as glass throughput on a toughening line may be increased.
• a higher coefficient of thermal expansion may allow for a reduction in the toughening temperature and/or a reduction in the quench pressure used to quench (cool) the hot glass and "fix" the desired compressive and tensile stresses into it.
• a glass plate according to the invention may be satisfactorily toughened or semi- toughened when provided in a thinner thickness (of less than 3.5 mm, or less than 3 mm) using conventional toughening equipment and processes (where specialised equipment is currently required to toughen such thin glasses of standard composition). The thinner the glass plate, the greater the weight reduction that may be achieved, and the greater the radiation transfer through it, which is especially useful for a cover glass plate.
• a solar unit comprising at least one glass plate as hereinbefore described.
• this at least one glass plate will usually be the cover plate of the unit.
• a photovoltaic solar unit preferably comprises at least two glass plates, each as individually hereinbefore described.
• the glass plates will usually be a cover plate and a backing plate.
• the backing plate is made of glass, this will normally be toughened to provide additional mechanical strength at a given thickness.
• the backing plate is made of thin glass to reduce the weight of the solar unit.
• the solar unit may also be a solar mirror for use in solar energy collection, comprising a curved glass plate which faces the sun.
• the curvature is selected to suit the focussing effect desired, e.g. it may be parabolic.
• the mirror may be a second surface mirror.
• the sun-facing glass plate may constitute a lens for use in solar collection, e.g. a Fresnel lens made by etching the plate.
• both plates are also made thinner than conventional glass plates, the overall weight of a photovoltaic solar unit will be reduced compared to an otherwise identical prior art unit, along with the described efficiency improvements. Weight reduction is likewise very important in solar mirror applications especially where these are mounted on tracking systems which follow the sun's orbit. Many solar thermal systems are mounted on the roofs of buildings. It is advantageous in these systems to reduce the units' weight in order to reduce the structural support required for them.
• the invention encompasses the novel glass compositions per se which are disclosed in this specification, regardless of their application.
• Example 1 is a known magnesia-containing flat glass composition
• Example 2 is a magnesia- free composition. Table I lists details of the measured compositions, ferrous levels, and position of the maximum of the ferrous absorption band for each composition.
• Example 1 is a prior art glass containing 0.12 % by weight total iron in a typical base glass composition, which notably includes approximately 13 % soda, 9 % calcia and 4 % magnesia, and is devoid of strontia and baria.
• the ferrous level of this glass is 20 % (measured chemically, as described earlier) and the maximum of the ferrous absorption band is located at 1040 nm - a position which interferes with transmission of radiation through to photovoltaic material when the glass is mounted as a cover glass in a photovoltaic unit.
• Example 2 illustrates the effect of removing MgO on the ferrous absorption band, producing a modest shift of 75 nm; the MgO has been replaced largely by CaO.
• Examples 3 to 7 are all glasses illustrative of the invention. These glasses can all be directly compared with Example 1 because they all contain the same amount of total iron as the glass of Example 1. Each of these glasses has its ferrous maximum at a longer wavelength position than that of Example 1; the longest wavelength value being 1150 nm in Examples 6 and 7 (exhibiting a shift of 110 nm).
• Examples 3 to 7 contain an increased total amount of alkali metal oxide compared to Example 1 , which is wholly due to an increased soda level. Furthermore, all contain decreased calcia and magnesia levels compared to Example 1 - calcia is decreased by at least 16 % whilst magnesia is decreased by at least 29 % - both being significant minimum reductions. Moreover, all contain a significant amount of strontia or baria. It should also be noted that the ferrous maximum is shifted to a higher wavelength with each successive addition of baria.
• a further refinement to this technique is to weight the transmission spectrum with the cell response of the particular photovoltaic material of interest.
• the benefit of the change in glass composition compared to a conventional prior art composition was calculated using the following opto-electrical modelling method.
• the model is based on a generalised picture of a photovoltaic cell in which light enters the cell through a cover glass, passes through a polymeric interlayer (if appropriate) and then falls on the photovoltaic material itself.
• the changes to the short-circuit current that arise from changing the transmission through, and/or reflection from, the glass are estimated. To do this, the fraction of incident light that is transmitted to the cell is calculated as a function of wavelength.
• a weighting factor based on the quantum efficiency (or spectral response) of a particular photovoltaic material is subsequently applied, for example as outlined in chapter two of "Solar Cells - Materials, Manufacture and Operation", edited by Tom Markvart and Luis Castaner, published by Elsevier 2005.
• the expected change in the short-circuit current can then be used to estimate a change in the cell efficiency.
• the transmission of the glass weighted by both the incoming light intensity and the cell response is calculated (summed over all wavelengths). This quantity is subsequently normalised by the light intensity and the cell response, again summed over all wavelengths.
• Table II shows the relative efficiency improvement predicted for some different types of photovoltaic material with each of the new glass compositions described in Table I above.
• the illustrative example materials include single crystal silicon wafer (c-Si) and thin film materials - amorphous (a-Si) and polycrystalline ( ⁇ c-Si) silicon both individually as single junction and combined as a tandem (multiple layer) junction cells, cadmium telluride (CdTe) and copper indium gallium diselenide (CIGS). All data is for samples 3.2mm in thickness. It should be understood that there may be similar benefits to photovoltaic cells manufactured from other materials e.g. gallium arsenide(GaAs).
• GaAs gallium arsenide
• the benefits for photovoltaic materials which absorb over a spectral range extending further into the infrared are expected to be even greater than for the illustrative examples given here as these materials are more susceptible to the adverse effects of the ferrous absorption band than the illustrative examples given.
• the benefits in concentrator systems utilising mirrors comprising of glass as described in this invention are expected to show a large efficiency benefit over conventional prior art glass as the solar radiation must make a double pass through the glass to the reflective layer and thence to the solar energy collection device.
• Examples 5, 6 and 7 contain baria.
• the baria is partially substituted for both magnesia and lime and in Examples 6 and 7 the magnesia is completely replaced by baria.
• Examples 6 and 7 show the largest shift in the position of the ferrous band maximum of 110 nm to 1150 nm as compared with example 1.
• comparison of Example 6 with Example 1 shows that, for nominally the same ferrous level and, surprisingly, nominally the same DSHT value, shifting the ferrous band maximum from 1040 nm to 1150 nm results in an improvement of the photovoltaic material weighted transmission of at least 0.3 percentage points, and typically 0.4 to 0.7 percentage points for materials other than a-Si.
• the typical efficiencies of crystalline silicon wafer based modules are currently (2009) around 15 - 18% and the thin film modules 6 - 11%.
• a relative efficiency improvement of 0.5% could lead to an increase in the module selling price of $1.3 - 4.1/m2 depending on the photovoltaic material used.
• the selling price increase depends upon both the photovoltaic material efficiency and the relative change in efficiency generated through the glass composition changes disclosed in this invention.
• the solar industry is developing rapidly and photovoltaic material efficiencies are likely to increase in the future.
• the selling prices of solar energy is likely to fall.
• the overall selling price benefit of improved efficiency generated through these composition changes is expected to remain around this level for some years.
• Example 7 illustrates the effect that the ferrous level of a glass has on its PMWT - here the glass has the same composition as the glass in Example 6, but its ferrous level is 26 % (compared to 20 % in Example 6).
• the negative values (i.e. worsening) on the PMWT of the glass of Example 7 illustrates that for this glass, the ferrous level is too high.
• the ferrous level of a glass depends on a number of factors, including the actual composition of each of the raw materials used and the temperature of the glass furnace in which the glass is made, each of which should be managed to keep the ferrous level at an acceptably low level (as described earlier) to achieve the type of benefits shown above in Table II.

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• 2008
  • 2008-06-09 GB GBGB0810525.6A patent/GB0810525D0/en not_active Ceased
• 2009
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  • 2009-06-09 JP JP2011513053A patent/JP2011522770A/ja active Pending
  • 2009-06-09 US US12/737,069 patent/US20110073182A1/en not_active Abandoned
  • 2009-06-09 WO PCT/GB2009/050640 patent/WO2009150451A1/en not_active Ceased
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