Obtaining Cullet from Thin Film Solar Modules
20200282432 ยท 2020-09-10
Inventors
Cpc classification
H01L31/0296
ELECTRICITY
B02C23/38
PERFORMING OPERATIONS; TRANSPORTING
Y02W30/52
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
B02C21/00
PERFORMING OPERATIONS; TRANSPORTING
Y02E10/50
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
H01L31/0445
ELECTRICITY
H01L31/0488
ELECTRICITY
B07C5/342
PERFORMING OPERATIONS; TRANSPORTING
B07C5/3427
PERFORMING OPERATIONS; TRANSPORTING
B02C23/10
PERFORMING OPERATIONS; TRANSPORTING
International classification
B07C5/342
PERFORMING OPERATIONS; TRANSPORTING
B02C21/00
PERFORMING OPERATIONS; TRANSPORTING
B02C23/10
PERFORMING OPERATIONS; TRANSPORTING
Abstract
A method of obtaining cullet from a solar module unit is disclosed. The method involves providing a solar module unit in which a detectable tagging material has been applied onto an exposed outer surface of a glass substrate of the solar module unit over one or more electrically conductive contact strips located beneath and visible through the glass substrate. Thereafter, the solar module unit is crushed into assorted module pieces. The assorted module pieces are then sorted by detecting module pieces that include the detectable tagging material and separating the assorted module pieces into a collection of accepted module pieces and a collection of rejected module pieces. The collection of accepted module pieces has module pieces determined not to include the detectable tagging material. Recycled glass is then obtained from the collection of accepted module pieces.
Claims
1. A method of obtaining cullet from a solar module unit, the method comprising: providing a solar module unit in which a detectable tagging material has been applied onto an exposed outer surface of a glass substrate of the solar module unit over one or more electrically conductive contact strips located beneath and visible through the glass substrate; crushing the solar module unit into assorted module pieces; sorting the assorted module pieces by detecting module pieces that include the detectable tagging material and then separating the assorted module pieces into a collection of accepted module pieces and a collection of rejected module pieces, the collection of accepted module pieces having module pieces determined not to include the detectable tagging material and the collection of rejected module pieces having module pieces determined to include the detectable tagging material; and obtaining recycled glass from the collection of accepted module pieces.
2. The method set forth in claim 1, wherein the detectable tagging material establishes a color differential against an adhesive layer adhered to an inner surface of the glass substrate and within which the one or more electrically conductive contact strips are embedded.
3. The method set forth in claim 2, wherein sorting the assorted module pieces comprises optically detecting the module pieces that include the detectable tagging material based on the color differential established between the detectable tagging material and the adhesive layer.
4. The method set forth in claim 1, wherein the detectable tagging material comprises one or more of a fugitive dye, a fluorescent dye, a carbon black ink, an organic or inorganic pigmented coating, metal flakes, or a colored tape.
5. The method set forth in claim 1, wherein the one or more electrically conductive contact strips are composed of solder-coated copper, and wherein the recycled glass obtained from the collection of accepted module pieces has a copper concentration of less than 10 ppm based on weight.
6. The method set forth in claim 1, wherein the method further comprises: refining the assorted module pieces after crushing the solar module unit, but prior to sorting of the assorted module pieces, to reduce the average piece size of the assorted module pieces.
7. The method set forth in claim 1, wherein the method further comprises: refining the collection of accepted module pieces after sorting of the assorted module pieces.
8. The method set forth in claim 1, wherein the solar module unit comprises a thin film Cd/Te photovoltaic system.
9. The method set forth in claim 1, wherein the solar module unit comprises an a-Si photovoltaic system.
10. The method set forth in claim 1, wherein the solar module unit comprises a CIGS photovoltaic system.
11. A method of obtaining cullet from a solar module unit, the method comprising: providing a solar module unit that includes a photovoltaic circuit that is encapsulated by an adhesive layer and further includes a glass substrate, the solar module having a detectable tagging material applied onto an exposed outer surface of the glass substrate over one or more electrically conductive contact strips located beneath and visible through the glass substrate on which the detectable tagging material is applied; crushing the solar module unit into assorted module pieces; sorting the assorted module pieces by detecting module pieces that include the detectable tagging material and then separating the assorted module pieces into a collection of accepted module pieces and a collection of rejected module pieces, the collection of accepted module pieces having module pieces determined not to include the detectable tagging material and the collection of rejected module pieces having module pieces determined to include the detectable tagging material; and removing adhered portions of the photovoltaic circuit and adhered portions of the adhesive layer from collection of accepted module pieces to isolate and obtain recycled glass from the collection of accepted module pieces.
12. The method set forth in claim 11, further comprising: refining the assorted module pieces before detecting which module pieces include the detectable tagging material to reduce the average piece side of the assorted module pieces.
13. The method set forth in claim 11, further comprising: refinging the collection of accepted module pieces after separting the assorted module pieces into the collection of accepted module pieces and the collection of rejection module pieces,
14. The method set forth in claim 11, wherein the photovoltaic circuit comprises a semiconductor layer of cadmium sulfide paired with a semiconductor layer of cadmium telluride.
15. The method set forth in claim 11, wherein the detectable tagging material establishes a color differential against the adhesive layer within which the one or more electrically conductive contact strips are embedded, and wherein sorting the assorted module pieces comprises optically detecting the module pieces that include the detectable tagging material based on the color differential established between the detectable tagging material and the adhesive layer
16. A method of obtaining cullet from a thin film solar module unit, the method comprising: providing a thin film solar module unit that includes a photovoltaic circuit that is encapsulated by an adhesive layer and sandwiched between a front glass substrate and a back glass substrate, the photovoltaic circuit comprising a semiconductor layer of cadmium sulfide paired with a semiconductor layer of cadmium telluride, the thin film solar module further having a detectable tagging material applied onto an exposed outer surface of the front or back glass substrate over one or more electrically conductive contact strips located beneath and visible through the front or back glass substrate on which the detectable tagging material is applied; crushing the thin film solar module unit into assorted module pieces; sorting the assorted module pieces by detecting module pieces that include the detectable tagging material and then separating the assorted module pieces into a collection of accepted module pieces and a collection of rejected module pieces, the collection of accepted module pieces having module pieces determined not to include the detectable tagging material and the collection of rejected module pieces having module pieces determined to include the detectable tagging material; leaching the accepted module pieces in a leaching solution to extract semiconductor materials into a leachant and detach adhered portions of the photovoltaic circuit and adhered portions of the adhesive layer from the collection of accepted module pieces to thereby isolate and obtain recycled glass from the collection of accepted module pieces; and reclaiming the semiconductor materials from the leachant.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] The disclosure, together with additional objects, features, advantages, and aspects thereof, will be best understood from the following description, the appended claims, and the accompanying drawings, in which:
[0013]
[0014]
[0015]
[0016]
[0017]
[0018]
DETAILED DESCRIPTION
[0019] The disclosed method of obtaining cullet from a thin film solar module unit involves selectively tagging an exposed outer surface of a glass substrate of the module unit over one or more electrically conductive contact strips visible through the glass substrate. Such tagging is performed by the application of a detectable tagging material that, for example, is optically detectable. The application of the detectable tagging material allows the module unit to be crushed and the resultant assortment of module pieces to be sorted based on the detection/non-detection of the tagging material. In this way, the module pieces that have the detectable tagging material, and thus may include remnants of the electrically conductive contact strip(s) following crushing, can be identified and separated from the rest of the module pieces prior to further processing of the module pieces to ultimately isolate and obtain recycled glass (i.e., cullet). By removing the module pieces tagged with the detectable tagging material, the cullet yielded by the disclosed method is low iron flint cullet of the soda-lime-silica variety that contains little to no contamination attributed to the contact strip(s). This type of cullet has flexible applications in the glass forming industry as it can be used in the raw material feedstock for both flint and colored glass articles.
[0020] Referring now to
[0021] A thin film photovoltaic circuit 16 is sandwiched between the front and back glass substrates 12, 14 and is encapsulated by an adhesive layer 18 that bonds the inner surfaces 12a, 14a of the glass substrates 12, 14 together. An edge seal (not shown) may also surround the peripheral edge of the photovoltaic circuit 16 in the constructed module 10. The photovoltaic circuit 16 may be based on any thin film photovoltaic system. For example, as described below in more detail, the thin film solar module 10 may be a Cd/Te module. The term Cd/Te as used herein refers to a module in which the semiconductor package of the photovoltaic circuit 16 comprises an n-type window semiconductor layer (i.e., a negative, electron donating layer) of cadmium sulfide (CdS) paired with a p-type absorber semiconductor layer (i.e., a positive, electron accepting layer) of cadmium telluride (CdTe) to establish a p-n heterojunction that drives an electrical current flow when sunlight (hv) passes through the front glass substrate 12 and is absorbed by the cadmium telluride semiconductor layer to create electron-hole pairs. While the thin film solar module 10 may include a Cd/Te thin film photovoltaic system within the photovoltaic circuit 16, other types of thin film systems may also be employed in lieu of a Cd/Te system, such as an a-Si (amorphous silicon) photovoltaic system or a CIGS (copper indium gallium selenide) photovoltaic system.
[0022] Referring now to
[0023] The front contact 20 may be one or more layers of transparent conductive oxides (TCO) such as a layer of indium tin oxide (ITO) deposited on the inner surface 12a of the front glass substrate 12 and a layer of tin oxide and/or zinc oxide deposited on the ITO layer. The CdS and the CdTe semiconductor layers 22, 24 are respectfully comprised of cadmium sulfide and cadmium telluride, as mentioned before, and are treated as necessary (e.g., annealing in chlorine atmosphere and chemical etching of CdTe) to give those layers 22, 24 their n-type and p-type functionality. The back contact 26 may be one or more layers of metal or another electrically conductive material such as a layer of zinc tellurium (ZnTe) alloy deposited on the CdTe semiconductor layer 24 and a layer of molybdenum deposited on the ZeTe alloy layer. Lastly, the adhesive layer 18, which encapsulates the photovoltaic circuit 16 to protect the photovoltaic circuit 16 from exposure to dirt and humidity, may be comprised of ethyl vinyl acetate (EVA). The adhesive layer 18 is also bonded to the inner surfaces 12a, 14a of the front and back glass substrates 12, 14 in order to hold the front and back glass substrates 12, 14and thus the module 10together. Other types of TCO's, electrically conductive materials, and adhesives may of course be used for the front contact 20, the back contact 26, and the adhesive layer 18, respectively, despite not being explicitly enumerated here.
[0024] The photovoltaic circuit 16 of the Cd/Te module 10 is preferably superstrate configured. A superstrate configuration refers to the fact that the photovoltaic circuit 16 is fabricated onto the inner surface 12a of the front glass substrate 12 in layered fashion with the understanding and expectation that the front glass substrate 12 will be directly exposed to sunlight (hv) when the resultant module is operational. In other words, during the manufacture of the module 10, the front contact 20 is first deposited onto the inner surface 12a of the front glass substrate 12. The n-type CdS semiconductor layer 22 is then deposited onto the front contact 20 and the p-type CdTe semiconductor layer 24 is deposited onto the n-type CdS semiconductor layer 22. After the semiconductor layers 22, 24 are in place, the back contact 26 is deposited onto the p-type CdTe semiconductor layer 24. Various thin film deposition techniques can be used to deposit the thin film layers 20, 22, 24, 26 including vapor transport deposition, chemical bath deposition, close-space sublimation, sputtering, and electrodeposition, among others.
[0025] The photovoltaic circuit 16 is subdivided into multiple monolithically integrated thin film solar strip cells 28 (only a few of which are identified in
[0026] In the presently disclosed Cd/Te module embodiment, and as shown in
[0027] The expected life of the thin film solar module 10 is currently in the neighborhood of about twenty to twenty five years. Upon exceeding its useful life, the module 10 is decommissioned and recycled. The glass forming industry is interested in obtaining cullet from the front and back glass substrates 12, 14 of the module 10, which can be an economical and dependable source of low iron cullet on the order of 10-15 kilograms per module, while the solar industry is interested in recovering semiconductor material, especially cadmium telluride. A major challenge involved in recycling the thin film solar module 10, however, is that the glass derived from present recycling efforts are often contaminated with remnants of the electrically conductive contact strip(s) 32. These remnants, particularly if they are remnants of solder-coated copper bus bars and/or interconnect bars, may be undesirable to the glass forming industry if present at too high of a concentration in the obtained cullet. The disclosed method can help minimize the contamination of cullet with remnants of the electrically conductive contact strip(s) 32. Referring now to
[0028] In the tagging material application step 52, a thin film solar module unit 100, which can be either the complete thin film solar module 10 or a smaller section of the module 10, is provided for recycling. The thin film solar module unit 100 thus has the same thin film layers and materials (or portions thereof) arranged in the same way as the thin film solar module 10 described above and, as such, the same reference numerals used in
[0029] The detectable tagging material 62 is formulated so that, when applied to the exposed outer surface 14b of the back glass substrate 14, it establishes a color differential against the adhesive layer 18 that is recognizable through optical detection. The established color differential that results from the selective application of the detectable tagging material 62 supports the subsequent sorting step 58 since the adhesive layer 18 and the embedded electrically conductive contact strip(s) 32 are otherwise difficult to distinguish based on color, particularly in those instances when the adhesive layer 18 comprises EVA and the contact strip(s) 32 are solder-coated copper bus bars 34 and interconnect bars 36. In addition to establishing a color differential against the adhesive layer 18, the detectable tagging material 62 should also bond strongly enough to the exposed outer surface 14b of the back glass surface 14 so that it can survive the crushing and refining steps 54, 56 that precede the sorting step 58 in the embodiment of
[0030] A number of different substances may serve as the detectable tagging material 62. In preferred embodiments of the tagging material application step 52, for example, the detectable tagging material 62 may comprise a fugitive dye, a fluorescent dye, a carbon black ink, an organic or inorganic pigmented coating, a paint, or metal flakes, to name but a few options. Moreover, if needed, the detectable tagging material 62 may also include, but is not required to include, other ingredients that support application and adhesion to the exposed outer surface 14b of the back glass substrate 14 such as at least one of the following: one or more dispersants, one or more surfactants, one or more polymers, one or more adhesion promoter additives, and/or one or more solvents. In another embodiment, the detectable tagging material may be a colored tape including, for example, duct tape or a specialty colored organic tape that is commercially available from 3M Company.
[0031] After the back glass substrate 14 has been tagged, the thin film solar module unit 100 is crushed in the crushing step 54 into assorted module pieces 66, a grouping of which are shown representatively in
[0032] The assorted module pieces 66 include glass from either the front glass substrate 12 or the back glass substrate 14; that is, some of the assorted module pieces 66 include a portion 12 of the front glass substrate 12 while others include a portion 14 of the back glass substrate 14, as illustrated in
[0033] The assorted module pieces 66 produced in the crushing step 54 fall into one of two categories: (1) module pieces 66a that include the detectable tagging material 62 (also referred to as tagged module pieces) and (2) module pieces 66b that do not include the detectable tagging material 62 (also referred to as untagged module pieces), as is further illustrated in
[0034] Following the crushing step 54, the assorted module pieces 66 may be refined, if needed, in the refining step 56 to further reduce the average piece size of the module pieces 66, for example, to between 4 mm and 10 mm. The assorted module pieces 66 may be further refined in an effort to limit the amount of untagged glass that may be present in the tagged module pieces 66a; in other words, if the assorted module pieces 66 have a smaller average piece size, there is less of a chance the tagged module pieces 66a will be accompanied by appreciable amounts of glass that is not tagged, thus improving the amount of cullet recoverable by the recycling method 50. In a preferred embodiment, the refining of the assorted module pieces 66 may be performed by a hammer mill. A typical hammer mill has a rotor mounted to a shaft and a drum that surrounds the rotor. The rotor supports a plurality of hammers that extend radially beyond the circumference of the rotor. When the hammer mill is operational, the assorted module pieces 66 are fed into the interior of the drum, which may include a grinding screen or grate, while the rotor and the drum are experiencing relative rotation. The relatively rotating drum and rotor hammers impact and crush the module pieces 66 to a smaller average piece size before the module pieces can exit the hammer mill. Of course, other mechanisms for refining the assorted module pieces 66 may be employed besides hammer milling.
[0035] Next, following the refining step 56, the assorted module pieces 66 are sorted in the sorting step 58. The sorting step 58 involves detecting the tagged module pieces 66a and then, based on the detection response, separating the assorted module pieces 66 into a collection of accepted module pieces 68 and a collection of rejected module pieces 70, as shown schematically in
[0036] As alluded to above, the collection of accepted module pieces 68 are those module pieces 66 that have been determined through detection not to include the detectable tagging material 62, and the collection of rejected module pieces 70 are those module pieces 66 that have been determined through detection to include the detectable tagging material 62. In that regard, the collection of accepted module pieces 68 includes all or a vast majority, i.e., greater than 80% by weight, of the untagged module pieces 66b, and the collection of rejected module pieces 70 includes all or a vast majority, i.e., greater than 80% by weight, of the tagged module pieces 66a. While perfect separation of the assorted module pieces 66 may not always be attainable in the sorting machinedue mainly to the fact that the sorting machine may operate with some acceptable margin of errormost if not all of the module pieces 66 that include remnants of the electrically conductive contact strips 32 are nonetheless identified through the applied detectable tagging material 62 and segregated into the collection of rejected module pieces 70. To improve the sorting accuracy of the sorting step 58, the sorting achieved by the glass sorting machine may, if needed or desired, be supplemented by hand sorting the collection of accepted module pieces 68 to remove any tagged module pieces 66a that may have evaded detection or separation in the sorting machine.
[0037] After the sorting step 58, recycled glass (i.e., cullet) 72 in particulate or piece form is obtained from the collection of accepted module pieces 68 in the cullet processing step 60. To obtain the recycled glass 72, the glass portions 12 from the front glass substrate 12 and the glass portions 14 from the back glass substrate 14 are isolated by removing adhered portions 16 of the photovoltaic circuit 16 and adhered portions 18 of the adhesive layer 18, respectively, from their surfaces. Such processing may involve leaching the accepted module pieces 68 in a leaching solution. For instance, in a preferred embodiment, the accepted module pieces 68 are added to a rotating leaching drum that includes a leaching solution comprising sulfuric acid and hydrogen peroxide. The leaching solution extracts the CdS and CdTe semiconductor materials to form a leachant 74 and, additionally, detaches any other materials (e.g., other portions 16 of the photovoltaic circuit 16 and portions 18 of the adhesive layer 18) from their respective glass portions 12, 14. Eventually, after several hours, the leachant 74 is drained from the leaching drum into a classifier and the cleaned glass portions 12, 14 are separated from other loose materials on a vibrating screen. The cleaned glass portions 12, 14 are then rinsed to remove any residual materials to thereby produce the recycled glass 72 in a condition suitable for use as feedstock cullet in subsequent glass forming operations. As for the leachant 74, it and the rinse solution are further processed to reclaim semiconductor material for use by the solar energy industry.
[0038] The recycled glass 72 obtained from the recycling method 50 is low iron (less than 0.015 wt % Fe) soda-lime-silica glass that has flexible applications in the glass forming industry including use in a raw material feedstock for both flint and colored glass articles. And because remnants of the electrically conductive contact strip(s) 32 are largely excluded from the collection of accepted module pieces 68, the recycled glass 72 obtained from the recycling method 50 is not overly contaminated from material of the electrically conductive contact strip(s) 32. For example, when the electrically conductive contact strip(s) 32 are composed of solder-coated copper, the concentration of copper in the obtained recycled glass 72 is less than 10 ppm by weight or, more narrowly, less than 5 ppm by weight. The term ppm by weight means parts weight per million total parts weight (e.g., 10 ppm by weight can be stated as 10 grams per million total grams). Maintaining a low concentration of copper or other contact strip materials in the recycled glass 72 helps preserve the chemical integrity of the glass melt in which the recycled glass 72 is later incorporated and, as a result, contributes to the minimization of commercial variations in manufactured glass articles.
[0039] The recycling method 50 depicted in
[0040] There thus has been disclosed a method of obtaining cullet from a thin film solar module unit that satisfies one or more of the objects and aims previously set forth. The disclosure has been presented in conjunction with several illustrative embodiments, and additional modifications and variations have been discussed. Other modifications and variations readily will suggest themselves to persons of ordinary skill in the art in view of the foregoing discussion. For example, the subject matter of each of the embodiments is hereby incorporated by reference into each of the other embodiments, for expedience. The disclosure is intended to embrace all such modifications and variations as fall within the spirit and broad scope of the appended claims.