AU2005270739B2

AU2005270739B2 - Photoelectrochemical Photovoltaic Panel and method to manufacture thereof

Info

Publication number: AU2005270739B2
Application number: AU2005270739A
Authority: AU
Inventors: Michael Peter John Bertoz; Graeme Leslie Evans; George Phani; Igor Lvovich Skryabin; Gavin Edmund Tulloch
Original assignee: Dyesol Ltd
Current assignee: Dyesol Ltd
Priority date: 2004-08-11
Filing date: 2005-08-11
Publication date: 2009-12-24
Anticipated expiration: 2025-08-11
Also published as: AU2005270739A1

Description

WO 2006/015431 PCT/AU2005/001194 -1 Photoelectrochemical Photovoltaic Panel and Method to Manufacture thereof. 5 TECHNICAL FIELD This invention relates to photoelectrochemical photovoltaic cells (PPC) . More particularly, the invention relates to photoelectrochemical photovoltaic modules of large size (both flexible and rigid) that include 10 plurality of the PEC integrated in one photovoltaic source. Examples of the PEC are disclosed in the following patent specifications: US4927721, Photoelectrochemical cell; Michael Graetzel and 15 Paul Liska, 1990. US5350644, Photovoltaic cells; Michael Graetzel, Mohammad K Nazeeruddin and Brian O'Regan, 1994. US5525440, Method of manufacture of photo-electrochemical cell and a cell made by this method; Andreas Kay, Michael 20 Graetzel and Brian O'Regan, 1996. US5728487, Photoelectrochemical cell and electrolyte for this cell; Michael Graetzel, Yordan Athanassov and Pierre Bonhote, 1998. WO 98/05084, Photoelectrochemical cell, S. Brodie et all. 25 US6297900- Electrophotochromic Smart Windows and Methods, Gavin Tulloch and Igor Skryabin, 2000. US6555741- Methods to Implement Interconnects in Multi cell Regenerative Photovoltaic Photoelectrochemical Devices, G.Phani, I.Skryabin and J.Hopkins, 2001 30 US6664623 - Methods to Implement Sealing and Electrical Connections to Single Cell and Multi-cell Regenerative Photovoltaic Photoelectrochemical Devices, G.Phani, J.Hopkins, D.Vittorio, I.Skryabin, 2002 WO 2006/015431 PCT/AU2005/001194 -2 BACKGROUND OF THE INVENTION Photoelectrochemical Photovoltaic Cells (PPC), as of 5 the type disclosed in the above patents, are typically fabricated in a laminate arrangement between two substrates. In a typical arrangement, at least one substrate is transparent to visible light and comprises a transparent support (typically glass for rigid modules and 10 plastic - for flexible modules) to which a transparent electrically conductive (TEC) coatings is applied. Another substrate is not necessarily transparent to visible light. Various materials suitable for non-transparent substrate are described in the prior art, including: 15 e Thin metallic films supported by glass, ceramic or polymer, * Metallic foils, * Metallic mesh, * Carbon based conductors. 20 However, the TEC coatings, which usually comprise a metal oxide(s), have high resistivity when compared with normal metal- conductors, resulting in high resistive losses for 25 large area cells. Thus, in practical application, these cells are combined in modules. Dimensions of the modules are limited, however, by necessity to maintain uniform thickness of a module 30 (typically 20-50 micrometers). In order to make a large photovoltaic photoelectrochemical panel (PPP) the modules are electrically connected and laminated between two additional large panes, one of which is being transparent.

WO 2006/015431 PCT/AU2005/001194 -3 (see, for example, Australian design No2093/2002). Manufacture of such panels, however, requires additional manufacturing equipment and procedures. 5 OBJECTIVE OF THE INVENTION 'Objective of this invention is to provide cost effective large size. photovoltaic photoelectrochemical panel. 10 SUMMARY OF THE INVENTION Generally the present invention provides for a Photoelectrochemical Photovoltaic Panel (PPP) comprising one shared substrate and a number of individual 15 substrates. The shared substrate is an electrical conductor or is at least partially coated by an electrically conducting material. Similarly, individual substrates are all electrical conductors or at least partially coated with an electrically conducting material. 20 In one embodiment the shared substrate is transparent to at least a part of solar radiation. In another embodiment at the individuals substrates are all transparent to at least a part of solar radiation. In further embodiment the individual substrates and 25 the shared substrate (hereafter - the substrates) are all transparent tolat least a part of solar radiation. In yet a further embodiment said electrically conducting material is a transparent electronic conductor (TEC), for example fluorine doped tin oxide or indium-tin 30 oxide. Photoelectrochemical photovoltaic cells (PPC) are formed between the shared substrate and the individual WO 2006/015431 PCT/AU2005/001194 -4 substrates. Each PPC includes a photosensitive electrode, a counter electrode and an electrolyte dispensed between the photosensitive electrode and the counter electrode. The photosensitive electrode typically comprises nano 5 particulate wide band semiconductor (for example titanium dioxide), photosensitised by a thin layer of dye. .In one embodiment the photosensitive electrodes of the PPC are supported by the shared substrate whereas the 10 counter electrodes of the PPC - by the individual substrates. In another embodiment only some of the photosensitive electrodes are supported by the shared substrate and the remaining photosensitive electrodes are 15 supported by the individual substrates. In the practical realisation of the invention the shared substrate is substantially larger than each of the individual substrates allowing for a significant number of 20 PPC to be formed in one panel. Although the invention has no specific restrictions on the shape of the shared substrate, rectangular shape is advantageous for the purpose of use and manufacture, especially - for roll-to roll manufacture, which is preferable when the shared 25 substrate 'and all the individual substrates are made of flexible material. In' one aspect of the invention, the shared substrate is divided into electrically isolated regions; each region 30 opposes at least one adjacent individual substrate and the PPC are formed between the individual substrate and the opposing isolated region of the shared substrate.

WO 2006/015431 PCT/AU2005/001194 -5 In one embodiment in accordance with this aspect of the invention at least one of the substrates is made of glass coated by Transparent Electronic Conductor (TEC). In another embodiment in accordance with this aspect 5 of the invention, at least one of the substrates is made of polymeric material coated by TEC. In still another embodiment, at least one of the substrates is made of metal or metal alloy. Preferential metals include titanium, tungsten, nickel, zinc or alloys 10 such as stainless steel. In yet another embodiment at least one of the substrates is made of metal coated by impermeable nitride (e.g. TiN). . In a further embodiment, at least one of the 15 substrates comprises metal foil or metallic mesh. In still a further embodiment, at least one of the substrates comprises polymeric sheet coated by metal or laminated-with metallic foil. In yet a further embodiment the shared substrate 20 comprise polymeric material coated by TEC and all the individual substrates comprise metal foil. In the preferred embodiment the shared substrate is made of polymeric material coated by TEC and all the individual substrates comprise metallic foil, wherein said 25 photosensitive electrodes of said PPC are formed on the individual substrates and counter electrodes - on the shared substrate. The invention provides for various shapes and dimensions of the individual substrates, it is 30 preferential, however, to utilise the individual substrates (and PPC electrodes) of circular shape in order to minimise resistive losses. Another advantage of the circular shape is in minimisation of perimeter for a given WO 2006/015431 PCT/AU2005/001194 -6 area of the PPC electrodes, since each of the PPC needs to be sealed along the perimeter of the individual substrate. Dimensions of each PPC depend on the type of conductor. Dimensions of the individual substrate depend on 5 resistivity of selected TEC material. It has been established that for full sun operations diameter of each PPC must not exceed 10-15 mm if resistivity of the TEC material is around 10 Ohms/square. In the preferred embodiment the individual substrates 10 are. electrically connected to selected electrically isolated regions of the common substrate. This allows for electrical connections between the PPC to form two terminal power source of the PPP. It is advantageous to connect the PPC in such a way that both negative and 15 positive terminals of the power source are located on the shared substrate. In another aspect of the invention a pattern of a second electrically conductive material is created on at 20 least one substrate. This material is selected to have conductivity higher than that of the first electrically conductive material. The second electrically conductive material enhances conductivity of the substrate without significant . reduction of its optical transparency. 25 Examples of the secondary conductive material include metal (for example, Ag, Cu, Au) tracks deposited on the substrate using screen-printing, vacuum mask deposition, electroplating, etc. In one embodiment, the electrically conductive 30 material is protected by an impermeable protective layer of glazing or polymeric material. This protection is especially important when said electrically conductive material is exposed to said electrolyte of PPC.

WO 2006/015431 PCT/AU2005/001194 -7 In another embodiment the pattern of the second electrically conductive material is created by varying the thickness of the first conducting material in such a way that regions of the substrate where high optical 5 transmittance is required (under or opposite the photosensitive electrodes) are coated by the relatively thin TEC (the first electrically conductive material), whereas other regions of the substrates, where high electrical conductance is required, are coated by a thick 10 electrically conductive material or (the second electrically conductive material). According to another aspect of the invention, small holes are prepared either in the shared substrates or in the common substrate. The holes are used for filling the 15 cells with said electrolyte. The holes are further sealed with a polymeric material, preferably by the laminate that comprises a hot melt polymeric material and a metal foil. From yet a further aspect of the invention, at least one 20 isolated. region of the shared substrate is further subdivided into electrically isolated subregions and the opposing individual substrate is also divided into electrically isolated subregions, with each said PPC being farmed between parts of two opposing subregions (one on 25 the shared substrate and another on the indvidual substrate) and said adjacent PPC are electrically interconnected in series by an interconnecting material. To enable connections of cells in series, the interconnecting material is placed between a separate part 30 of the sub region adjacent to the photosensitive electrode of n-th said PPC and a separate part of the sub region adjacent to said counterlectrode of (n+1)-th PPC.

WO 2006/015431 PCT/AU2005/001194 -8 In one embodiment the interconnecting material comprises metallic particles, and/or graphite flakes. In another embodiment the said interconnecting material comprises metal wire, wire braid or wire plait. 5 In yet another embodiment the said electrically interconnecting material comprises metallic mesh. In a further embodiment electrically conducting components of the interconnecting material are protected from electrolyte of PPC by impermeable electrically 10 insulating material, preferably - polymeric material, in which said conducting components are embedded. In the preferred embodiment said polymeric material is hot melt material. 15 In one process the insulating hot melt material is melted and adhered to both substrates due to the heat generated in metallic interconnecting material. The invention provides for passing electrical current through the interconnecting material in order to generate heat 20 sufficient for. melting and adhesion of the hot melt material. In preferred process the heat is generated by an inductive action of an electromagnetic field. Specific attention is given to the spaces that formed 25 between the individual substrates when they attached to the common substrate. In one embodiment these spaces are filled with an hermetic sealant. In another embodiment humidity absorbing material 30 (e.g. - molecular sieves) is placed in these spaces; to ensure long term stability of the photoelectrochemical devices.

WO 2006/015431 PCT/AU2005/001194 -9 In yet another embodiment these spaces are fully or partially filled with a solvent of the same chemical nature as that used for an electrolyte in the photoelectrochemical cells. This is to minimise long term 5 degradation effects caused by the loss of solvent. in the cells. BRIEF DESCRIPTION OF DRAWINGS 10 Having broadly portrayed the nature of the present invention, embodiments thereof will now be described by way of example and illustration only. In the following description, reference will be made to the accompanying drawings in which: 15 Figure 1 is a 3D diagrammatic representation of a PPP formed in accordance with the first example of the invention. Figure 2 is an enlarged partial cross- section of a Photoelectrochemical Photovoltaic Panel formed in 20 accordance with the first example of the invention. Figure 3 is an enlarged partial cross-sectional view of a PPP formed in accordance with the second example of the invention. Figure 4 is a partial plan representation of a PPP 25 formed in accordance with the second example of the invention. Figure 5 is a 3D diagrammatic representation of the flexible shared substrate of PPP formed in accordance with the third example of the invention. 30 Figure 6 is a 3D diagrammatic representation of the flexible PPP formed in accordance with the third example of the invention.

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Received 13 July 2006 - 10 DETAILED DESCRIPTION OF DRAWINGS 5 With reference to Figure 1, a 3D diagrammatic representation of a PPP is shown. The panel comprises twelve individual substrates I and a shared substrate i. The substrates are coated by TEC (fluorine doped tin oxide) layer 3. The 10 electrically isolated regions of the transparent electrical conductor 3 are formed by removing said conductor along the isolation lines 4. This procedure utilizes laser radiation and can be applied to all the substrates; 3D representation in Fig. 1 allows visualisation of these lines only on the 15 shared substrate. The PPC are formed between parts of the isolated regions 5 of the common substrate and opposing isolated regions of the isolated substrate. The PPC are interconnected to form 2 terminal power output of the PPP. The terminals are created by depositing Ag bus-bars 6. Also 20 shown a plane A, cross-sectional representation in which is shown in Figure 2. With reference to figure 2, cross section that includes three individual glass substrates is shown. The shared substrate 1 25 (also-glass) and the individual substrates 2 are coated by TEC layer 3- The electrically isolated regions are formed by removing TEC material along the lines 4. Counter electrodes 7 (ultra-thin layer of Pt based catalyst) is formed on parts of the electrically isolated regions of the individual 30 substrates 2, using standard screen-printing technique. Photosensitized electrodes a are formed on parts of the isolated regions Amended Sheet TDTP A /A YT X '- i/lVU/fU/UI IY4 Received 13 July 2006 - 11 3a of the shared substrate 2. The photosensitized electrodes 8 comprise nano-particulate layer of titanium dioxide. (15 microns thick) photosensitized by Ru-based dye. Formation (by screen-printing followed by firing) and. 5 photosensitization of the nano-particulate layer of titanium dioxide was performed in accordance with standard procedures well known in the prior art. The PPC were interconnected by interconnecting material 9 that comprises W particles embedded into silicone based matrix and filled by redox 10 electrolyte 10 through small filling holes in the shared substrate (not shown). External negative and positive terminals 6 are created by application of Ag bus-bars. With reference to Fig. 3, cross-sectional representation of 15 the second example depicts only one individual substrate 2. All the numbered elements in this figure are as per Fig. 1 and Fig. 2. This example is different from the first example of the invention in that the photosensitized electrodes here are formed on the individual substrates and counter 20 electrodes - on the common substrate. With reference to Figure 4 a partial planar view of a PPP depicting only 1 individual substrate is presented. Additionally, sealing material 11 and filling holes 12 are 25 shown. The holes were used for- vacuum back filling of the . cells with an electrolyte. With reference to Figure 5 a shared flexible substrate 1 is prepared in accordance with third example of the invention. 30 The substrate comprises plastic sheet coated by transparent electronic conductor 3. The transparent Amended Sheet TPPA ATT PCT/AU2005/001194 Received 13 July 2006 -12 Electronic conductor 3 is divided into four electrically isolated regions by the isolation lines 4. To enhance electrical conductor of TEC material and to provide for electrical connection four Ag bus-bars 6 are deposited onto 5 the TEC as shown in the figure. On parts of three (out of four) isolated regions of the shared substrate the circularly shaped counter electrodes 7 are formed such as 8 equally spaced counter electrodes belong to each of the three isolated regions. This will provide for B PPC in each 10 isolated region of the shared substrate that will be connected in parallel. Three groups of 8 PPC will be connected in series as further demonstrated in- Figure 6. With reference to Figure 6 a flexible PPP is prepared in 15 accordance with the third example of the invention. The patent utilizes pre-prepared shared substrate (shown in details. in Fig. 5) and 24 individual substrates 2. Each individual substrate comprises Ti foil, on which a photosensitized electrode is formed. The individual 20 substrates sealed with the shard substrate in such a way that the photosensitive electrodes of the individual substrates oppose counter electrodes of the shared substrates. The 24 PPC are formed by filling spaces between the photosensitized electrodes and opposing counter electrodes with a redox 25 electrolyte. The cells are connected in parallel in groups of three by ext(i-nal electrical connectors 13 and in series (in groups of 3) by electrical jumps 14. The positive and negative electrical terminal of the PPP are also shown. Amended Sheet

TPRA/ATT

Claims

1. A photoelectrochemical Photovoltaic Panel (PPP) comprising a number of individual substrates and a shared substrate (the substrates), wherein the substrates are electrical conductors or at least partially coated by an electrically conducting material, at least the shared substrate or all of the individual substrates are substantially transparent to at least a part of solar radiation (optically transparent), at least two of the individual substrates are provided on the same side of the shared substrate, Photoelectrochemical Photovoltaic Cells (PPC), each comprising a photosensitive electrode, a counter electrode and an electrolyte dispensed between the photosensitive electrode and the counter electrode are formed between the shared substrate and the individual substrates

2. A PPP according to claim 1, wherein at least one substrate comprises optically transparent material coated by a Transparent Electrical conductor (TEC) .

3. A PPP according to claim 2, wherein said optically transparent material comprise glass or plastic.

4. A PPP according to claim 2 and claim 3, wherein said TEC comprises fluorine doped tin oxide, indium tin oxide or metallic mesh.

5. A PPP according to claim 1, wherein all the substrates are optically transparent.

6. A PPP according to claim 1, wherein the shared substrate comprises metal sheet or foil and all the individual substrates are optically transparent.

7. A PPP according to claim 1, wherein the individual substrates comprise metal sheet or foil and the shared substrate is optically transparent.

8. A PPP in accordance with claim 1, wherein said photosensitive electrode comprises nano-particulate wide band semiconductor (for example - titanium dioxide), Iu/AUZUUf')/UU1194 Received 13 July 2006 -14 photosensitised by a thin layer of dye and electrically connected to one of the substrates or its electrically conducting material 9.. A PPP in accordance with claim 1, wherein said 5 photosensitive electrodes of PPC are supported by the shared substrate.

10- A PPP in accordance with claim 1, wherein at least a part of said photosensitive electrodes of PPC are supported by the shared substrate and photosensitive electrodes of 10 remaining PPC are supported by the individual substrates.

11. A PPP in accordance with claim 1, wherein said shared substrate is of rectangular shape.

12. A PPP in accordance with claim 1, wherein said individual substrates are of rectangular or circular shape. 15 13. A PPP in accordance with claim 1, wherein the shared substrate is divided into electrically isolated regions; each region opposes at least one adjacent individual substrate and the PPC are formed between the individual. substrate and the opposing isolated region of the shared 20 substrate.

14. A PPP in accordance with any one of claim 13, claim 4 or claim 7, wherein the shared substrate is made of polymeric material coated by TEC and all the individual substrates comprise metallic foil, wherein said 25 photosensitive electrodes of said PPC are formed on. Amended Sheet T1f'f A I. T WO 2006/015431 PCT/AU2005/001194 -15 the individual substrates and counter electrodes - on the parts of said electrically isolated regions of the shared substrate.

15. A PPP in accordance with claim 14, wherein the 5 individual substrates are electrically connected to selected electrically isolated regions of the common substrate.

16. A PPP in accordance with claim 2, wherein electrical conductance of TEC material is enhanced by application 10 of a pattern of second. electrically conductive material.

17. A PPP in accordance with claim 16, wherein said pattern of the second conducting material comprises metallic tracks formed on TEC layer. 15 18. A PPP in accordance with. claim 17, wherein said metallic tracks are protected by an impermeable protective layer of glazing or polymeric material.

19. A PPP in accordance with claim 16 wherein said second conductive material is created by increasing the 20 thickness of TEC coating in such a way that regions of the substrate where high optical transmittance is required (under or opposite the photosensitive electrodes) are coated by the relatively thin TEC (the first electrically conductive material), whereas other 25 regions of the substrates, where high electrical conductance is required, are coated by a thick TEC (the second electrically conductive material).

20. A PPP in accordance with claim 13 wherein small holes are prepared in the individual and/or shared 30 substrates; said holes being used for filling the PPC with the electrolyte. WO 2006/015431 PCT/AU2005/001194 -16

21. A PPP in accordance with claim 20, wherein after filling the PPC with the electrolyte the holes are sealed by a polymeric material.

22. A PPP in accordance with claim 21, wherein said 5 polymeric material comprises hot melt material laminated with metallic foil.

23. A PPP in accordance with claim 13, wherein at least one isolated region.of the shared substrate is further subdivided into electrically isolated subregions and 10 the opposing individual substrate is also divided into electrically isolated subregions, with each said PPC being formed between parts of- two opposing subregions (one on the common substrate and another on the separate substrate) . and said adjacent PPC are 15 electrically interconnected in series by . an interconnecting material.

24. A PPP in accordance with claim 23, wherein the interconnecting material is placed between a separate part of the sub region adjacent to photosensitive 20 electrode of n-th said PPC and a separate part of the sub region adjacent to counterelectrode of (n+l)-th PPC.

25. A PPP in accordance with claim 23, wherein said interconnecting material comprises metallic particles 25 and/origraphite flakes.

26. A PPP in accordance with claim 23, wherein interconnecting material comprises metal wire, metallic mesh, wire braid or wire plait.

27. A PPP in accordance with claim 25 or claim 26 wherein 30 said interconnecting material is protected from electrolyte of PEC by impermeable electrically insulating material, preferably - polymeric material, in which said conducting components are embedded. WO 2006/015431 PCT/AU2005/001194 -17

28. A PPP in accordance with claim 27, wherein said polymeric 'material is hot melt material.

29. A PPP in accordance with claim 28, wherein said hot melt is melted and adhered to the opposing substrates 5 due to the heat generated in the interconnecting material.

30. A PPP in accordance with.claim 29, wherein the heat is generated by an~ inductive action of electromagnetic field. 10 31. A PPP in accordance with claim 13 wherein spaces that formed between the individual substrates when they are attached to the. shared substrate are sealed with a hermetic sealant.

32. A PPP in accordance with claim.31, wherein said spaces 15 are filled with a humidity absorbing material such as molecular sieves. 20 25 30 35