CN101355187B

CN101355187B - Photoelectric converter

Info

Publication number: CN101355187B
Application number: CN 200810147288
Authority: CN
Inventors: 江连哲也; 田边信夫; 松井浩志; 冈田显一
Original assignee: Fujikura Ltd
Current assignee: Fujikura Ltd
Priority date: 2003-08-06
Filing date: 2004-08-03
Publication date: 2010-07-28
Anticipated expiration: 2024-08-03
Also published as: CN101355187A; CN100536224C; CN101355186A; CN1830115A; CN101355186B; CN101452771B; CN101452771A

Abstract

Disclosed is a photoelectric converter which comprises a case and a laminated body housed in the case. The laminated body comprises a working electrode, a counter electrode, and an electrolyte layer arranged between the working electrode and the counter electrode. The laminated body also comprises a case overlaying the laminated body; and a cover, fixing the cascade body on the case, wherein, the case overlaying the area corresponding to a position formed with an electric conductor on the working electrode.

Description

Photo-electric conversion element

The application is according to the applying date: on August 3rd, 2004, application number: 200480021802.5, denomination of invention: what photo-electric conversion element and manufacture method thereof proposed divides an application.

The application is willing to 2003-No. 421084 for the spy that the spy is willing to 2003-No. 288076 and on December 18th, 2003 applied for of application on August 6th, 2003; On December 25th, 2003, the spy of application was willing to 2003-No. 430606; On March 5th, 2004, the spy of application was willing to 2004-No. 63032; On March 31st, 2004, the spy of application was willing to 2004-No. 106616; And the spy of on March 31st, 2004 application is willing to advocate priority 2004-No. 106617, quotes its content at this.

Technical field

The present invention relates to photo-electric conversion element and manufacture methods thereof such as dye-sensitized solar cell.Specifically, relating to can be to having the battery body of the duplexer that forms with the utmost point is clipped dielectric substrate with the effect utmost point, do not apply loads such as heating, and with photo-electric conversion element and the manufacture method thereof of battery component parts with the encapsulation material Integratively sealing that is disposed at its outside, and will be a plurality of with the effect utmost point and the utmost point is clipped the photo-electric conversion element that the overlapping duplexer that forms of electrolytical state is arranged in the basket and is sealed.

Background technology

Under backgrounds such as environmental problem, resource problem, gazed at by people as the solar cell of clean energy resource.As solar cell, the type of using single crystals, many crystallizations or amorphous silicon is arranged.But silicon in the past is that solar cell has problems such as manufacturing cost height and raw material supplying deficiency, therefore fails to popularize.

And, developing Cu-In-Se system series of compounds solar cells such as (being also referred to as CIS system) now, this series of compounds solar cell has excellent features such as demonstrating high conversion efficiency.Yet this series of compounds solar cell also fails to popularize because of problems such as cost and environmental pressures.

For above-mentioned solar cell, the dye-sensitized solar cell of institute's motions such as group of people such as the ゲレッ Star ェ Le of Switzerland is as cheap and can obtain the photo-electric conversion element of high-photoelectric transformation efficiency and receive publicity.

Fig. 1 represents the pattern cutaway view of an example of the dye-sensitized solar cell of prior art.

This dye-sensitized solar cell 100 is mainly by constituting with the lower part: be formed with the 1st substrate 101, the 2nd substrate 105 that is formed with conducting film 104 that carry the porous semiconductor electrode holding sensitizing coloring matter (below be also referred to as dye-sensitized semi-conducting electrode) 103 on the face, enclose between the aforesaid substrate for example by dielectric substrate 106 that gel-like electrolyte was constituted.

In the 1st substrate 101, use the sheet material of light transmission, give conductivity, be provided with transparency conducting layer 102 for the face that joins with dye-sensitized semi-conducting electrode 103 to the 1st substrate 101.Constitute the window utmost point 108 by the 1st substrate 101, transparency conducting layer 102 and dye-sensitized semi-conducting electrode 103.

On the other hand, on the 2nd substrate 105, for to giving conductivity, for example be provided with conductive layer 104 by carbon or platinum constituted with the join face of side of dielectric substrate 106.Constitute the utmost point 109 by the 2nd substrate 105 and conductive layer 104.

In dye-sensitized solar cell 100, according to make dye-sensitized semi-conducting electrode 103 and conductive layer 104 relative to mode, the 1st substrate 101 and the 2nd substrate 105 are disposed across predetermined space, and the periphery between two substrates is provided with the sealant 107 that is made of thermoplastic resin.Can enumerate following structure, promptly fit two substrates 101,105 and form battery by sealing agent 107, see through the inlet 110 of electrolyte and between the two poles of the earth 108,109, fill the oxidation that comprises iodine, iodide ion etc./go back the organic electrolyte of original seed, and form the dielectric substrate 106 that electric charge is transferred usefulness.That is, sealant 107 plays the effect of spilling of the electrolyte that prevents to be included in the dielectric substrate 106 or volatile ingredient volatilization.

Next illustrates the summary situation of the manufacture method of dye-sensitized solar cell 100.

At first, by by sealing material 107 that thermoplastic resin constituted and the laminated glazing utmost point 108 with to after the utmost point 109, by the window utmost point 108 and to the utmost point 109 or the window utmost point 108 or to either party and heated sealant material 107 in the utmost point 109, and make its fusion, thereby the unbonded window utmost point 108 with to the utmost point 109, form the duplexer that constitutes by pair of electrodes (the window utmost point 108 with to the utmost point 109).

Then, see through to run through and to comprise iodine the inlet 110 of the utmost point 109 ground settings, the electrolyte of oxidations such as iodide ion/go back original seed is filled in the window utmost point 108 and to after between the utmost point 109, clog inlet 110 with lid 111, form electric charge and transfer the dielectric substrate 106 of usefulness, and obtain by pair of electrodes (the window utmost point 108 with to the utmost point 109), and be clipped in dye-sensitized solar cell 100 that the dielectric substrate 106 between the above-mentioned electrode constituted (for example with reference to 2002-No. 184478 communiques of TOHKEMY, and N.Papageorgiou et al., J.Electrochem.Soc., 143 (10), 3099,1996).

As the injection mode of this electrolyte, can be after assembling the battery unit of solar cell, utilize capillarity, pressure differential etc. and inject from the liquid injection port of being located at the back side etc. with intermittent mode.

Following report is also arranged, promptly have the perforated membrane structure of the coefficient of roughness, improve absorptivity and obtain photoelectric conversion efficiency more than 10% greater than 1000 high surface area ratio by the semiconductor utmost point is set as.Being contemplated for existing silicon aspect the cost is about 1/2～1/6 of solar cell, not necessarily need complexity, large-scale manufacturing equipment, and do not contain hazardous substance, therefore, have higher possibility as being adapted to a large amount of cheapnesss of popularizing, a large amount of type of production solar cell.

But, in the above-mentioned dye-sensitized solar cell, volatile solvents such as acetonitrile are enclosed battery as the electrolyte use and with it, this series has the problem that produces the battery behavior reduction because of volatilization.Therefore attempt using ionic liquid as electrolyte (for example with reference to N.Papageorgiou et al., J.Electrochem.Soc., 143 (10), 3099,1996) as its countermeasure.This ionic liquid is also referred to as normal temperature meltbility salt, is the salt that stable liquid exists, only just is being made of with the ion of negative electrical charge band near the wider temperature range comprising room temperature.In fact this ionic liquid does not have vapour pressure, needn't worry as organic solvent volatilize like that, on fire etc., therefore be can be used as by waiting in expectation solution because of volatilization the means that reduce of the battery behavior that causes.

And, use under the situation of electrolyte, might be during fabrication or battery spill electrolyte when damaged, therefore as the countermeasure that prevents leakage, each research institution is just prevailing and is using suitable gelating agent and electrolyte is given gelation (plan solidification).(for example 2002-No. 184478 communiques of TOHKEMY).After the gelation of carrying out is also arranged, the report that more can suppress to volatilize than the situation of liquid condition.Also carry out same test for ionic liquid, and have all good advantage of fail safe, durability through the ionic liquid (ion glue) of gelation.

Yet, in the manufacturing of above-mentioned dye-sensitized solar cell in the past, use thermoplastic resin to seal and form sealant 107.As shown in Figure 1, particularly, heating and molten resin and two plate electrodes that bond (the window utmost point 108, to the utmost point 109).This moment, heat was passed to dye-sensitized semi-conducting electrode 103 via the 1st substrate 101, therefore might produce harmful effect to the pigment that is adsorbed on the dye-sensitized semi-conducting electrode 103.

And sealant 107 is formed by resin, so when long-term the use, have the problem of weatherability.

And, when injecting electrolyte, heat bonding two plate electrode plates and form the shape of battery at first, see through the inlet 110 of opening in advance then and inject the electrolyte between two plate electrodes of delimiting narrow space extremely, on inlet 110, add loam cake 111 at last, therefore manufacturing process's complicated problems is arranged.And, if electrolyte viscosity height then must spend many times and time in order to inject electrolyte, therefore can cause increasing manufacturing cost.

And sealing material 107 is made of thermoplastic resin, so weatherability is poor, so the problem that is unsuitable for long-term use is arranged.

Summary of the invention

The 1st mode of the present invention is In view of the foregoing finished, its purpose is to provide a kind of photo-electric conversion element and manufacture method thereof, the heat that this photo-electric conversion element and manufacture method thereof are applied in the time of can being suppressed at the bonding electrode is to being adsorbed in the influence that pigment caused of dye-sensitized semi-conducting electrode, weatherability excellence during long-term simultaneously the use, and can carry out aqueous or gelatinous electrolytical filling easily.

The 1st mode of the present invention provides a kind of photo-electric conversion element, and this photo-electric conversion element has duplexer; And take in the basket of aforementioned duplexer, aforementioned duplexer has: the effect utmost point is provided with the oxide semiconductor porous layer that sensitizing coloring matter is supported at the surface in one face; To the utmost point, with the aforementioned effect utmost point aforementioned one in the face of to configuration; Dielectric substrate, it is formed at the aforementioned effect utmost point and aforementioned between the utmost point; And electric conductor, its mode according to the side that surrounds aforementioned oxide semiconductor porous layer is provided with, and aforementioned basket has: framework, it covers aforementioned duplexer; And lid, it is fixed in aforementioned framework with aforementioned duplexer, and wherein, aforementioned framework covers in aforementioned effect extremely and the corresponding zone, position that is formed with aforementioned electric conductor.

In the above-mentioned photo-electric conversion element, with the effect utmost point with the utmost point is clipped dielectric substrate and the duplexer that forms, with above it and below contact the inner face of basket directly or indirectly and be contained.Promptly, no matter be directly or indirect state, all constitute inner face by basket sandwich the top of duplexer and below, thereby can comprise the battery component parts that constitutes by duplexer in interior part by the sealing of sealing basket and Integratively, therefore can obviously reduce the influence of the heat that puts on duplexer.Therefore, can solve this problem in the past of predetermined function that hinders pigment owing to the influence that is subjected to the heat that the electrode bonding time applied, pigment can play consistently its performance, so can obtain stable light transfer characteristic.And, if constituted by the material that has through the optical characteristics of sunlight with the part that contacts of the effect utmost point at least in the basket, just sunlight can be taken in the battery component parts that is made of duplexer.

And, the photo-electric conversion element of this formation can utilize the duplexer that forms with the utmost point is clipped dielectric substrate with the effect utmost point, therefore after for example aqueous or gelatinous electrolyte being dripped, is coated with or is sprayed on a side the electrode, sandwich another electrode from it and exert pressure, can make aqueous or gelatinous electrolyte soak into the oxide semiconductor porous laminar surface of the effect utmost point in constituting electrode thus and form dielectric substrate, can form the duplexer that forms with the utmost point is clipped dielectric substrate with the effect utmost point thus.At this moment, being clipped in interelectrode aqueous or gelatinous electrolyte can not overflow from the gap because of capillarity.So, needed the electrolyte of many times injection process owing to can save in the past, therefore can further cut down and make the needed cost of photo-electric conversion element.

And, according to above-mentioned formation, owing to unnecessaryly used the sealant that constitutes by resin like that in the past, thus the weatherability can improve long-term the use time, so the photo-electric conversion element of the long-time stability excellence of light transfer characteristic can be provided.

And, above-mentioned photo-electric conversion element, employing will be arranged at by the battery component parts that duplexer constitutes in the basket and the structure that does not contact with extraneous air.That is, the battery component parts is accommodated in the airtight space, therefore can obtain to compare the photo-electric conversion element that the characteristic of corresponding environment is more excellent with photo-electric conversion element in the past.

In the above-mentioned photo-electric conversion element, by elastomeric element being set between to the utmost point and aforementioned basket, and the duplexer that forms with the utmost point is clipped dielectric substrate with the effect utmost point is kept in basket with the state that is pressed securely from above-below direction by the counter-force of elastomeric element aforementioned.So,, therefore can provide for external force to have high shape stability and the also excellent photo-electric conversion element of vibration strength because upper/lower electrode is difficult for direction generation relative position skew in face.

In above-mentioned photo-electric conversion element, employing is according to the mode that does not contact the side of aforementioned duplexer by aforementioned basket inside, divide the end that is arranged be connected to aforementioned to the utmost point with the aforementioned effect utmost point and the other end extends to the structure of aforementioned basket electric conductor outward respectively, then can will freely export to outside the basket in order to the other end of the electric conductor that is connected with external circuit any position from basket.Therefore, holding the photo-electric conversion element of the 1st mode of the present invention that the battery component parts that is made of duplexer forms in basket can be corresponding to the diversified condition that is provided with that cooperates the external circuit system.

As a preferred example of the other end of aforementioned electric conductor, can enumerate the structure that outside basket, extends from aforementioned basket side.According to this structure, under the situation that a plurality of photo-electric conversion elements are connected in series, only, therefore can significantly shorten the desired time of construction by according to the mode that contacts between each sidepiece of basket is got final product the configuration of basket two-dimensional arrangements.Particularly do not need in the past in order to connect the circuit between the photo-electric conversion element, so can become to make assembly to hang down.

And, as a preferred example of the other end of aforementioned electric conductor, can enumerate from the structure of aforementioned basket bottom extension to basket outside.According to this structure, under the situation that a plurality of photo-electric conversion elements are connected in series, only, therefore can significantly shorten the desired time of construction by the configuration of basket two-dimensional arrangements being got final product according to the mode that makes basket bottom contact external circuit.Particularly form the underlay of basket, so form the state of protecting external circuit with the basket of built-in photo-electric conversion element, therefore can further improve anti-environmental characteristics in order to the external circuit that connects between each photo-electric conversion element.

The photo-electric conversion element of this mode for example can be used as part or all of roof Material or wall material.

The 1st mode of the present invention provides a kind of manufacture method of photo-electric conversion element, and this manufacture method comprises following operation,, provides the operation of the basket that possesses casing and lid that is, and wherein casing has inner bottom surface; Provide and have the operation that makes sensitizing coloring matter be supported at the effect utmost point of surperficial oxide semiconductor porous layer; Aqueous or gelatinous electrolyte is filled on the aforementioned oxide semiconductor porous layer of the aforementioned effect utmost point and forms the operation of dielectric substrate; Operation with the aforementioned inner bottom surface of the aforementioned casing that the utmost point is disposed at aforementioned basket; The aforementioned effect utmost point is overlapped in aforementioned to the utmost point and make the aforementioned operation that the utmost point is formed duplexer of aforesaid electrolyte layer contact; The aforementioned lid that disposes aforementioned basket is to cover the operation of the aforementioned effect utmost point; Reach the operation that seals basket from the outside of aforementioned basket towards the direction imposed load vertical with aforementioned stacked surface.

In above-mentioned manufacture method, by aqueous or gelatinous electrolyte being filled in the operation that forms dielectric substrate on the oxide semiconductor porous layer that constitutes the aforementioned effect utmost point, aqueous or gelatinous electrolyte is distributed on the surface of oxide semiconductor porous layer equably.

At this, what is called is filled in aqueous or gelatinous electrolyte on the oxide semiconductor porous layer of the formation effect utmost point, comprises making aqueous or gelatinous electrolyte is soaked in the oxide semiconductor porous laminar surface.And so-called aqueous electrolyte refers generally to electrolyte, for electrolyte ingredients such as iodine, iodide ion are dissolved in the solution that solvent forms.

For example aqueous or gelatinous electrolyte is dripped, is coated with or is sprayed at the effect utmost point with to after on the electrode of the side in extremely, another electrode that sandwiches from it and exerting pressure, aqueous or gelatinous electrolyte is soaked in constituting electrode, act on the oxide semiconductor porous laminar surface of the utmost point and form dielectric substrate, can form the duplexer that forms with the utmost point is clipped dielectric substrate with the effect utmost point thus.

Promptly, according to this operation, do not need as in the past through inlet and with the aqueous or gelatinous electrolyte utmost point of injection effect forcibly and to the crawl space between the utmost point, therefore, can eliminate at the effect utmost point and between and produce the aqueous or gelatinous electrolytical field that to distribute, bad situations such as the local existence of aqueous or gelatinous electrolyte the utmost point.

And, be provided with aforementioned by inner bottom surface to the utmost point at the casing that constitutes basket, and so that the aforesaid electrolyte layer contact the overlapping aforementioned effect utmost point of this mode and form duplexer the utmost point, and dispose the lid that constitutes aforementioned basket in the mode that covers this effect utmost point, the direction imposed load vertical with aforementioned stacked surface and seal the operation of basket from aforementioned basket lateral can will comprise the part Integratively sealing of the battery component parts that is made of duplexer by the sealing basket then.Sealing is during basket, can heat duplexer hardly even basket heated also locally.Therefore, if adopt this operation, then can solve the influence that in the past was subjected to the heat that the electrode bonding time applied and hinder problem such as pigment intended function.

Therefore, the manufacture method of the 1st mode of the present invention helps stably to make the photo-electric conversion element with above-mentioned feature, promptly, the heat that is applied in the time of can being suppressed at the bonding electrode is to being adsorbed in the influence that pigment caused of dye-sensitized semi-conducting electrode, weatherability excellence during long-term simultaneously use the, and the photo-electric conversion element that can carry out aqueous or gelatinous electrolytical filling easily.

The 2nd mode of the present invention is In view of the foregoing finished, its purpose is to provide a kind of photo-electric conversion element and manufacture method thereof, this photo-electric conversion element and manufacture method thereof can be dripped electrolyte and be injected into dye-sensitized semi-conducting electrode, and can obtain excellent generating efficiency.

The 2nd mode of the present invention provides a kind of photo-electric conversion element, and this photo-electric conversion element has: the casing with inner bottom surface; And duplexer, aforementioned duplexer has: the effect utmost point, and it has makes sensitizing coloring matter be supported at the oxide semiconductor porous layer on surface; To the utmost point, it is in the aforementioned oxide semiconductor porous layer side and the configuration of aforementioned effect utmost point subtend of this effect utmost point; And dielectric substrate, it is disposed at the aforementioned effect utmost point and aforementioned at least a portion between the utmost point, wherein, aforementioned duplexer is accommodated in the aforementioned casing and aforementioned the utmost point is directly or indirectly contacted with the inner bottom surface of aforementioned casing, and this casing uses aforementioned effect extremely to seal.

In the photo-electric conversion element of this formation, to act on the duplexer that the utmost point forms with the utmost point is clipped electrolyte, to be incorporated in the casing and to make the utmost point is directly or indirectly contacted with inner bottom surface, and this casing extremely seals with effect.That is, effect utmost point double as constitutes the lid of basket.

Adopt the photo-electric conversion element of this formation can utilize the duplexer that forms with the utmost point is clipped electrolyte with the effect utmost point, therefore, can be by for example aqueous or gelatinous electrolyte being filled on a side the electrode, and form duplexer to sandwich another electrode from it.At this moment, being clipped in interelectrode electrolyte can not overflow from the gap because of capillarity.So can save needed the electrolyte of many times injection process in the past, therefore can further cut down and make the needed cost of photo-electric conversion element.

In above-mentioned photo-electric conversion element, the 1st substrate that constitutes the aforementioned effect utmost point preferably uses optical characteristics and the stable on heating material that has concurrently through sunlight.By having optical characteristics,, sunlight is accommodated in the interior duplexer of basket and fully being arrived through sunlight.And by having thermal endurance, the thermal impact that is subjected in the time of suppressing because of sealing produces situations such as warpage, can keep interelectrode distance, therefore can guarantee the long-time stability of power generation characteristics.

The 2nd mode of the present invention is to provide a kind of manufacture method of photo-electric conversion element, and this manufacture method has following operation,, provides the operation of the basket that possesses casing that is, and wherein casing has inner bottom surface; Provide and have the operation that makes sensitizing coloring matter be supported at the effect utmost point of surperficial oxide semiconductor porous layer; Aqueous or gelatinous electrolyte is filled in the aforementioned oxide semiconductor porous layer of the aforementioned effect utmost point and forms the operation of dielectric substrate; With the aforementioned inner bottom surface of the aforementioned aforementioned casing that the utmost point is disposed at aforementioned basket and make aforementioned to the extremely direct or indirect operation of the aforementioned inner bottom surface of the aforementioned casing of contact; The aforementioned effect utmost point is overlapped in aforementioned to the utmost point and make the aforementioned operation that the utmost point is formed duplexer of aforesaid electrolyte layer contact; This effect utmost point is configured to cover the operation of aforementioned basket; And utilize laser method or mull technique that the aforementioned effect utmost point is sealed in aforementioned casing and the operation of making aforementioned basket.

This manufacture method particularly has following operation, promptly, be provided with aforementioned to the utmost point and make its directly or indirectly contact constitute the inner bottom surface of the casing of basket, and, the aforementioned mode to the utmost point of aforesaid electrolyte layer contact aforementioned the utmost point is formed duplexer so that being overlapped in the aforementioned effect utmost point, and will act on after the lid that the utmost point is configured to aforementioned basket, the aforementioned effect utmost point is sealed in aforementioned casing and the operation of making aforementioned basket with laser method or mull technique, therefore, can keep and to inject electrolytical advantage by filling, can use resin as in the past, and only by the part (being called laser method) that will seal with laser radiation or binding agent (being called mull technique) is set just can be sealed easily.Promptly, in the manufacture method of the 2nd mode of the present invention, owing to the connecting portion of lid and casing only seals with laser radiation or bonding, therefore can be as encapsulating method in the past for battery itself, be that duplexer applies and heats or the load of pressurization etc., the duplexer that forms battery can be accommodated in the casing that constitutes basket, lid be set thereon and the basket Integratively is sealed.And, can also avoid taking place because of sealing resin spreads the bad situation that is caused, so preferred.

The 3rd mode of the present invention is In view of the foregoing finished, its purpose is to provide a kind of photo-electric conversion element, this photo-electric conversion element can obtain excellent generating efficiency, and can suppress the change of generating efficiency, and, on the whole sensitive surface of photo-electric conversion element, almost there be not the uneven of generating efficiency.

The 3rd mode of the present invention provides a kind of photo-electric conversion element, and this photo-electric conversion element is characterised in that to have: basket; And a plurality of duplexers, aforementioned a plurality of duplexers are arranged and are sealed in the aforementioned basket, and aforementioned each duplexer has: the effect utmost point; To the utmost point; And dielectric substrate, it is clipped in the aforementioned effect utmost point and aforementioned between the utmost point, and aforementioned basket has: backboard; And be located at the framework of the peripheral part of this backboard, aforementioned framework has side wall portion and window frame portion, aforementioned window frame portion and aforementioned backboard subtend dispose and aforementioned duplexer are pushed towards aforementioned backboard direction, aforementioned duplexer has the current collection wiring part, and aforementioned window frame portion is arranged on the corresponding zone, position with the aforementioned current collection wiring part of aforementioned duplexer.

The invention of the 3rd mode of the present invention is characterised in that aforementioned lateral wall portion is dismantled and assembled with respect to aforementioned backboard, or aforementioned window frame portion is dismantled and assembled with respect to aforementioned lateral wall portion.

The invention of the 3rd mode of the present invention is characterised in that, between aforementioned duplexer and aforementioned backboard elastomeric element is being set.

The 4th mode of the present invention is In view of the foregoing finished, and its purpose is to provide a kind of photo-electric conversion element, and this photo-electric conversion element can be made at an easy rate, and long-term reliability and generating efficiency excellence are repaired easily when bad situation takes place or changed.

For solving above-mentioned problem, the 4th mode of the present invention provides a kind of photo-electric conversion element, and this photo-electric conversion element has: duplexer; And take in the basket of aforementioned duplexer, aforementioned duplexer has: the effect utmost point; To the utmost point; And dielectric substrate, it is formed at the aforementioned effect utmost point and aforementioned between the utmost point, and aforementioned basket has: framework, it covers aforementioned duplexer; And lid, it is fixed in aforementioned framework with aforementioned duplexer, and wherein, aforementioned framework covers in aforementioned effect extremely and the corresponding zone, position that is formed with aforementioned electric conductor.

In above-mentioned photo-electric conversion element, preferred aforementioned electric conductor is located at the circumference of the aforementioned effect utmost point.

In above-mentioned photo-electric conversion element, preferred aforementioned lid removably is fixed on the aforementioned framework.

In above-mentioned photo-electric conversion element, preferably clip elastomeric element between to the utmost point and aforementioned lid aforementioned.

The 5th mode of the present invention is In view of the foregoing finished, and its purpose is to provide a kind of photo-electric conversion element, and this photo-electric conversion element can be made at an easy rate, and long-term reliability and generating efficiency excellence are repaired easily when bad situation takes place or changed.

For solving above-mentioned problem, the 5th mode of the present invention provides a kind of photo-electric conversion element, and this photo-electric conversion element has: duplexer; And take in the basket of aforementioned duplexer, aforementioned duplexer has: the effect utmost point; To the utmost point; And dielectric substrate, it is formed on the aforementioned effect utmost point and aforementioned between the utmost point, and aforementioned basket has: body, it covers aforementioned duplexer; And lid, it is fixed in aforementioned body with aforementioned duplexer, and wherein, aforementioned lid removably is fixed in aforementioned body.

The 5th mode of the present invention provides a kind of photo-electric conversion element, this photo-electric conversion element has by the effect utmost point, to the utmost point and be formed at the duplexer that dielectric substrate constituted between the above-mentioned utmost point, accommodate the basket of above-mentioned parts, and aforementioned basket is made of the body that covers aforementioned duplexer, and the aforementioned effect utmost point removably is fixed on the aforementioned body.

In above-mentioned photo-electric conversion element, preferably clip elastomeric element between to the utmost point and aforementioned basket aforementioned.

Description of drawings

Fig. 1 is the cutaway view of an example of the dye-sensitized solar cell of expression prior art.

Fig. 2 is the cutaway view of an example of the photo-electric conversion element of expression the 1st execution mode of the present invention.

Fig. 3 is another routine cutaway view of the photo-electric conversion element of expression the 1st execution mode of the present invention.

Fig. 4 is the cutaway view of an example of the photo-electric conversion element of expression the 1st execution mode of the present invention.

Fig. 5 is the cutaway view of an example of the photo-electric conversion element of expression the 2nd execution mode of the present invention.

Fig. 6 is that an example of the photo-electric conversion element of expression the 3rd execution mode of the present invention is the vertical view of dye-sensitized solar cell.

Fig. 7 is the cutaway view of A among Fig. 6-A line.

Fig. 8 is other routine cutaway view of the dye-sensitized solar cell of expression the 3rd execution mode of the present invention.

Fig. 9 is another routine cutaway view of the dye-sensitized solar cell of expression the 3rd execution mode of the present invention.

Figure 10 is that the 1st example of the photo-electric conversion element of expression the 4th execution mode of the present invention is the general profile chart of dye-sensitized solar cell.

Figure 11 is the approximate vertical view of the dye-sensitized solar cell of expression Figure 10.

Figure 12 is that the 2nd example of the photo-electric conversion element of expression the 4th execution mode of the present invention is the general profile chart of dye-sensitized solar cell.

Figure 13 is that the 1st example of the photo-electric conversion element of expression the 5th execution mode of the present invention is the general profile chart of dye-sensitized solar cell.

Figure 14 is that the 2nd example of the photo-electric conversion element of expression the 5th execution mode of the present invention is the general profile chart of dye-sensitized solar cell.

Embodiment

Following with reference to description of drawings the preferred embodiments of the present invention.But the present invention is not limited only to following each embodiment, and can for example make up each inscape of these embodiment aptly.

(the 1st execution mode)

Followingly describe the 1st execution mode of the present invention in detail according to embodiment.

Fig. 2 is the pattern cutaway view of an example of the photo-electric conversion element of expression the 1st execution mode of the present invention.

This dye-sensitized solar cell (photo-electric conversion element) 210 disposes: the dielectric substrate 216 to the utmost point 219 and at least a portion between above-mentioned the two poles of the earth that have the effect utmost point (being also referred to as the window utmost point) 218 that carries the oxide semiconductor porous layer (being also referred to as oxide electrode) 213 of holding sensitizing coloring matter on the surface, disposes in oxide semiconductor porous layer 213 side of the effect utmost point 218 and its subtend.The effect utmost point 218 is by for example the 1st substrate 211 and the nesa coating 212 and the oxide electrode 213 of arranged in order are constituted thereon.One side the utmost point 219 is made of with configuration conducting film 214 thereon for example the 2nd substrate 215.

The duplexer 220 that forms with the utmost point 219 is clipped dielectric substrate 216 with the effect utmost point 218 has the function of battery component parts, promptly has the function of photo-electric conversion element.In dye-sensitized solar cell 210, duplexer 220 is accommodated in the inboard of the basket 221 that surrounds this duplexer, the inner face of the top and following contact basket 221 of duplexer 220.The part of the utmost point of contact action at least 218 of basket 221, lid 225 promptly shown in Figure 2 is made of the material that has through the optical characteristics of sunlight.

In dye-sensitized solar cell 210, be accommodated above it and the following inner face that contacts basket 221 with the duplexer 220 that forms with the utmost point 219 is clipped dielectric substrate 216 of the effect utmost point 218, the inner face of basket 221 sandwiches below top the reaching of duplexer 220.Therefore, if the part that is contacted with the sidepiece 224 of casing 222 at for example lid 225 seals basket 221, just can comprise the part Integratively sealing of the battery component parts that is constituted by duplexer 220.

And, in Fig. 2, when representing to seal basket 221, the arrow of duplexer 220 puts on the direction of the power of duplexer 220.Lateral shift takes place in order to be suppressed on the duplexer 220 when in the direction duplexer 220 being applied external force, or, preferably between bottom 223, elastomeric element 226 is set to the utmost point 219 and formation basket 221 according to making duplexer 220 keep flexibility and the mode that firmly fixes seals duplexer 220 at above-below direction.

And, with same reason, between the lid 225 of the effect utmost point 218 and formation basket, insert gap filling material 227.But because gap filling material 227 is configured on the effect utmost point 218, pretending is the gap filling material 227 preferred materials through characteristic good that use sunlight.And if filling silicon oil as gap filling material 227, then can be removed the air layer that is present between the 1st substrate 211 and the lid 225, transparency improves, so preferred.

Elastomeric element 226 and gap filling material 227 are set, can suppress the relative position skew of upper/lower electrode direction in its face, can improve shape stability simultaneously, and can give vibration strength, so preferred for external force.

And, in dye-sensitized solar cell 210, adopted following formation: according to inner by basket 221 and do not touch the mode of the side of duplexer 220, branch offers an end and is connected to the utmost point 219 and the effect utmost point 218, and the other end extends to the electric conductor 228,229 outside the basket 221 respectively.

According to this structure, export to outside the basket owing to can freely will be used for connecting the other end of the electric conductor 228,229 of not shown external circuit from any position of basket 221, therefore can adapt to the diversified condition that is provided with of cooperation external circuit system.

For the end effect of the being connected in utmost point 218 and the other end extend to the outer electric conductor 228 of basket 221, for making it by the basket 221 inner sides that do not touch duplexer 220, for example as shown in Figure 2, can be set as the structure that between the side of duplexer 220 and electric conductor 228, sandwiches above-mentioned elastomeric element 226.Fig. 2 has represented that electric conductor 228 is sandwiched the example of elastomeric element 226 configuration with the sidepiece 224 of basket 221, runs through structure in the elastomeric element 226 yet also can be set as electric conductor 228.

Electric conductor 228,229 shown in Figure 2 constitutes its other end separately and extends to outside the basket 221 from the sidepiece 224 of basket 221.Adopt under the situation of this structure, only carry out the two-dimensional arrangements configuration according to contacted mode between the side that makes the basket that stores each photo-electric conversion element, a plurality of photo-electric conversion elements just can be connected in series.Do not need needed link and connecting circuit when connecting photo-electric conversion element fully, and only the alignment arrangements basket can connect, therefore the photo-electric conversion element of the 1st execution mode of the present invention can shorten the needed time of construction significantly in the past.And, owing to link and the connecting circuit that can save between each photo-electric conversion element, therefore can make with low cost.All form the photo-electric conversion element of the basket that clips duplexer, can replace glass pane to use with transparent component.

Fig. 3 is another routine pattern cutaway view of the photo-electric conversion element of expression the 1st execution mode of the present invention.Photo-electric conversion element 210 shown in Figure 3 except electric conductor 228 ', 229 ' the other end respectively beyond the bottom 223 of basket 221 extends to structure the basket 221, identical with photo-electric conversion element 210 shown in Figure 2.Adopt under the situation of this structure, only according to the mode two-dimensional arrangements configuration basket 221 of the bottom 223 contact external circuits that make basket 221, a plurality of photo-electric conversion elements just can be connected in series.Do not need needed link and connecting circuit when connecting each photo-electric conversion element fully in the past, and only can be connected photo-electric conversion element at the configuration of a side of mounting basket and electric conductor 228 ', 229 ' contact, therefore the photo-electric conversion element of the 1st execution mode of the present invention can shorten the needed time of constructing significantly.And, owing to link and the connecting circuit that can save between each photo-electric conversion element, therefore can make with low cost.Because the photo-electric conversion element of this structure can use, therefore for example can be used as part or all use of roof Material or wall material as roof tiles or ceramic tile.

The 1st substrate 211 as the 1st execution mode of the present invention, use is by the plate that material constituted of light transmission, as glass, PETG, PEN, Merlon, polyether sulphur etc., so long as the general material that uses as the transparency carrier of solar cell just can use.As long as consider to select aptly for aqueous or gelatinous electrolytical tolerance etc., but consider its purposes, it is good selecting the high substrate of light transmission as far as possible.

Preferably on the face of dye-sensitized semi-conducting electrode 213 sides of the 1st substrate 211, form the nesa coating 212 that is constituted by metal, carbon, conductive metal oxide layer etc. in advance, and give conductivity.Forming under metal level or the situation of carbon-coating, be preferably formed as the structure that undermines the transparency for not obvious,, selecting the kind of metal aptly from forming the viewpoint of the film that can not undermine the conductivity and the transparency as nesa coating 212.Can use for example ITO, SnO ₂, mix the SnO of fluorine ₂Deng as conductive metal oxide.

, on the transparency conducting layer 2 on the 1st substrate 211, and then be provided with and make the multichip semiconductor pore membrane carry the dye-sensitized semi-conducting electrode 213 of holding sensitizing coloring matter and forming in mounting.The formation effect utmost point (the window utmost point) 218 with the 1st substrate 211, transparency conducting layer 2 and dye-sensitized semi-conducting electrode 213.The semiconductor that forms the multichip semiconductor pore membrane of dye-sensitized semi-conducting electrode 213 is not particularly limited, so long as be generally used in the material of the porous semi-conductor that forms used for solar batteries, can use, and for example can use TiO ₂, SnO ₂, WO ₃, ZnO, Nb ₂O ₅Deng.But the method illustration that forms perforated membrane is removed the unnecessary method that becomes to grade after the mixture of the formation film based on sol-gal process, atomic swimming electro-deposition, the porous based on blowing agent, coating and polymer particles etc. is arranged, and still is not limited in this.

As sensitizing coloring matter, use is contained in second bipyridine structure, terpyridyl structure etc. in containing metal complex compounds such as the ruthenium complex, porphyrin, phthalocyanine dye of dentate, also can use organic pigments such as eosin, rhodamine, part cyanines etc., be not particularly limited aspect purposes, the use, and can selecting to have the material that is suitable for semi-conductive drive characteristic.

Owing to need not have light transmission especially, therefore can use metallic plate as the 2nd substrate 215, also can use and the 1st substrate 211 identical materials.Use is provided with the electrode conduct of conducting film 214 to the utmost point 219 on the 2nd substrate 215.Conducting film 214 can use the heat treatment behind for example evaporation, sputter, the coating chlorination platinic acid and the layer of the carbon that forms or platinum etc. so long as have electrode function, is not particularly limited.

At the above-mentioned effect utmost point 218 and between dielectric substrate 216 is set and forms the battery component parts that is constituted by duplexer 220 utmost point 219.As described later, the duplexer 220 of the 1st execution mode of the present invention forms by the following method: after aqueous or gelatinous electrolyte being dripped, is coated with or is sprayed on the oxide semiconductor porous layer 213 of the formation effect utmost point 218, according to making the aqueous or gelatinous electrolyte and the mode overlap action utmost point 218 that the utmost point 219 is contacted, and with the direction imposed load of duplexer Surface Vertical.

Therefore, the dielectric substrate 216 of the 1st execution mode of the present invention also can use the high material of viscosity that in the past was difficult to inject from inlet narrow electrode gap, therefore, can utilize as gelatinous electrolyte, use suitable gelating agent and aqueous electrolyte has been carried out gelation (plan solidification) and full-bodied material, employed in the past any material all can use.

As the material that constitutes aforesaid electrolyte layer 216, can enumerate: for example be dissolved in the aqueous electrolyte (being commonly referred to as electrolyte) that organic solvents such as ethylene carbonate or methoxyacetonitrile form, will gather as gelating agent and fluoridize that inferior ethene, polyethylene oxygen support derivative, amino acid derivativges etc. are added in the above-mentioned aqueous electrolyte and the gel-like electrolyte of gelation etc. as electrolyte ingredient and with iodine, iodide ion, tert .-butylpyridine etc.

The duplexer 220 that forms with the utmost point 219 is clipped dielectric substrate 216 with the effect utmost point 218 is accommodated in the basket 221 the inner face indirect contact that is top and following and basket 221 of duplexer 220.In the basket 221 at least with the effect utmost point 218 part of joining, to be lid 225 be made of the material that has through the optical characteristics of sunlight, for example can enumerate the material of transparent and tool rigidity such as propylene, Merlon, polyvinyl chloride, soda-lime glass.The other parts of basket 221, the casing 222 that promptly is made of bottom 223 and sidepiece 224 as long as can guarantee and the insulating properties of the electric conductor 228,229 of the external circuit that extends to basket 221 from two electrodes respectively, then do not limit its material especially.

Inner bottom surface at the casing 222 that constitutes basket 221 is provided with the utmost point 219, according to making dielectric substrate 216 form duplexer 220 with the mode overlap action utmost point 218 that the utmost point 219 is joined, and dispose according to the mode that covers this effect utmost point 218 after the lid 225 of formation basket 222, from the outside of basket 221 towards sealing basket 221 with the direction imposed load of duplexer 220 Surface Vertical, thereby obtain dye-sensitized solar cell 210.

The encapsulating method of basket 221 can be exerted pressure with the contact site of lid 225 or hot carrying out by the sidepiece 224 for for example basket 221.Though but duplexer 220 is accommodated in the basket 221, it is configured in the position of sealing place of leaving basket 221, and therefore, the heat that is produced by sealing can not influence duplexer 220.If for example seal, then can constitute the structure that does not use thermoplastic resin with laser.

And, after dripping, be coated with or be sprayed at the aqueous or gelatinous electrolyte that forms dielectric substrate 216 on the effect utmost point (the window utmost point) 218, overlapping from it to the utmost point 219 and to act on the utmost point 218 and the utmost point 219 to be clipped aqueous or gelatinous electrolyte and exert pressure, thereby can on the oxide semiconductor porous layer of the formation effect utmost point 218, fill aqueous or gelatinous electrolyte and form dielectric substrate 216, thus, can form the duplexer 220 that forms with the utmost point 219 is clipped dielectric substrate 216 with the effect utmost point 218.

Therefore, can omit as in the past perforate on to the utmost point 219, inject electrolyte, clog numerous and diverse operation such as hole, thus can simple manufacturing process and can cut down the labour, therefore can obtain photo-electric conversion element cheaply.And, owing to can be set as narrow than in the past with the effect utmost point (the window utmost point) 218 and to the distance between the utmost point 219, so can improve the generating efficiency of dye-sensitized solar cell.And, at the 1st substrate 211 of the formation effect utmost point (the window utmost point) 218 and constitute between the lid 225 of basket 221 filling silicon oil as gap filling material 227, just can remove the air layer that is present between the 1st substrate 211 and the lid 225, transparency rises, so preferred.

As described above, in the 1st execution mode of the present invention, the battery component parts that will be constituted with the duplexer 220 that the effect utmost point 218 forms with the utmost point 219 is clipped dielectric substrate 216 is accommodated in the basket.Therefore, if sealing basket, just can will comprise the part Integratively sealing of the battery component parts that is constituted by duplexer 220, therefore can obtain to avoid the photo-electric conversion element of the influence that problem in the past, the heat that applied when promptly boning electrode cause the pigment that is adsorbed in dye-sensitized semi-conducting electrode.And, because the battery component parts that constituted of duplexer 220 is accommodated in the basket, so the photo-electric conversion element of weatherability excellence when long-term use can be provided.And, in the 1st execution mode of the present invention, can before being accommodated in basket, make the duplexer 220 that forms with the utmost point 219 is clipped dielectric substrate 216 with the effect utmost point 218, so can carry out aqueous or gelatinous electrolyte easy as can to interelectrode injection, therefore help significantly to reduce manufacturing cost.

And, in the present embodiment, as dye-sensitized solar cell (photo-electric conversion element) 210, illustration between bottom 223, elastomeric element 226 is set to the utmost point 219 and basket 221, and acting on insertion gap filling material 227 between the utmost point 218 and the lid 225, the dye-sensitized solar cell (photo-electric conversion element) 210 of the interior surface construction of the top and following indirect contact basket 221 of duplexer 220, yet, also can be that elastomeric element 226 or gap filling material 227 are not set, and in basket 221, take in the dye-sensitized solar cell (photo-electric conversion element) of duplexer 220 according to the mode of the inner face that makes the top of duplexer 220 and following directly contact basket 221.And, also can be and arrange a plurality of duplexers 220 and be accommodated in structure in the basket 221.

(the 2nd execution mode)

Put down in writing the photo-electric conversion element 250 of the 1st execution mode of the present invention shown in Figure 4 above.This photo-electric conversion element 250 is improved based on two main points of view described below.

The 1st, can be suppressed at the influence of heat that bonding applies during electrode, and the weatherability when using for a long time is good, can carry out the injection of electrolyte easily to the pigment that is adsorbed in dye-sensitized semi-conducting electrode.

That is,,, therefore can avoid the influence of above-mentioned heat for pigment because heat does not put on directly that two plate electrodes promptly act on the utmost point 258 and to the utmost point 259 according to the structure of Fig. 4.And, by on the dye-sensitized semi-conducting electrode 253 that electrolyte is dripped and sandwiched, and can form the duplexer 260 that forms with the utmost point 259 is clipped electrolyte with the effect utmost point 258, therefore have the advantage of saving the operation of injecting electrolyte.And, because therefore the effect utmost point 258 and the inboard that the utmost point 259 is accommodated in basket 251 can not be subjected to direct impact from the outside, so have the advantage of guaranteeing for the intensity of external force yet.

The 2nd, the substrate that constitutes electrode can not produce distortion or damage, and can seal, and can establish the thickness of substrate very thin, and can also guarantee to be electrically connected stability.

Promptly, in photo-electric conversion element 250, according to inner by basket 251 and do not contact the mode of duplexer 260 sides, divide the end that is arranged to be connected to the utmost point 259 and the effect utmost point 258, the other end are extended to the electric conductor 268,269 outside the basket 251 respectively, thereby realize photo-electric conversion element 250 and outside being electrically connected.Particularly an end is connected in the electric conductor 268 of the effect utmost point 258, extend along the contact-making surface of the nesa coating 252 of the elastomeric element 266a between face that is disposed at duplexer 260 and the basket 261 and the formation effect utmost point 258 and to be provided with, can prevent electric conductor 268 short circuit with the contacts side surfaces of duplexer 260, even and elastomeric element 266a distortion when sealing, electric conductor 268 can not be subjected to its influence yet, thus the end that can guarantee electric conductor 268 with act on the stability that is electrically connected between the utmost point 258.

Be set as near the form that is not vulnerable to unbalanced pressure its end by acting on the utmost point 258 like this, can adopt thickness for example the glass substrate as thin as a wafer of 0.3mm therefore can further establish photo-electric conversion element 250 very thin as the 1st substrate 251 of the formation effect utmost point 258.

Followingly the 2nd execution mode of the present invention is described,, and is not limited to these examples as long as the 2nd execution mode of the present invention meets above-mentioned effect and effect according to embodiment.

Fig. 5 is the pattern cutaway view of an example of the photo-electric conversion element of expression the 2nd execution mode of the present invention.

This dye-sensitized solar cell (photo-electric conversion element) 310 disposes: the dielectric substrate 316 that the utmost point 319 and at least a portion between above-mentioned the two poles of the earth are disposed that has the effect utmost point (also claiming the window utmost point) 318 that carries the oxide semiconductor porous layer (also claiming oxide electrode) 313 of holding sensitizing coloring matter on the surface, disposes with its subtend in oxide semiconductor porous layer 313 side of the effect utmost point 318.The effect utmost point 318 is by for example the 1st substrate 311 and the nesa coating 312 and the oxide electrode 313 of arranged in order are constituted thereon.The electrode 319 of one side is made of with configuration conducting film 314 thereon for example the 2nd substrate 315.

The duplexer 320 that forms with the utmost point 319 is clipped dielectric substrate 316 with the effect utmost point 318 has the function of battery component parts, promptly has the function of photo-electric conversion element.In dye-sensitized solar cell 310, the part of the effect utmost point 318 i.e. the 1st substrate 311 works as a lateral electrode that forms battery, and the function of the lid of also performance formation basket.That is, duplexer 320 is accommodated in the inboard of the casing 322 and the basket that lid (the effect utmost point 318) is constituted of this duplexer of encirclement, and the inner bottom surface of the following and casing 322 of duplexer 320 joins.For constituting also the 1st substrate 311 of bringing into play the effect utmost point 318 of function as the lid of basket, the preferred material that has through the optical characteristics of sunlight that uses.

In dye-sensitized solar cell 310, to be accommodated with the duplexer 320 that the effect utmost point 318 forms with the utmost point 319 is clipped dielectric substrate 316 below it with the inner bottom surface of casing 322 promptly the inner face of bottom 323 join, the part of the effect utmost point 318 i.e. the 1st substrate 311 plays a role as lid.Be the bottom 323 of the casing 322 of duplexer 320 by forming basket in the dye-sensitized solar cell 310 with also as the 1st substrate 311 of lid constitutes clip above and following structure.

Therefore, the inner bottom surface that constitutes the casing 322 of basket according to direct or indirect contact is that the mode of the inner face of bottom 323 is provided with the utmost point 319, and according to making dielectric substrate 316 contact form duplexer 320 to the mode overlap action utmost point 318 of the utmost point 319, a part that makes the effect utmost point 318 is after the 1st substrate 311 constitutes the lid of baskets, seal in the part that the sidepiece 324 of the 1st substrate 311 of the effect utmost point 318 and casing 322 joins with laser method, can comprise the part Integratively sealing of battery component parts with duplexer 320.

The photo-electric conversion element 310 that adopts this formation is because of utilizing with the effect utmost point 318 and the utmost point 319 being clipped the duplexer 320 that dielectric substrate 316 forms, therefore can pass through for example on the electrode of a side, to fill aqueous or gelatinous electrolyte, and form duplexer with the electrode that sandwiches opposite side thereon.At this moment, being sandwiched in interelectrode electrolyte can not overflow from the gap because of capillarity.Therefore, the 2nd execution mode according to the present invention can be saved the operation of the injection electrolyte of many times of needs in the past, and therefore, the 2nd execution mode of the present invention helps to provide photo-electric conversion element cheaply.

And for above-mentioned photo-electric conversion element 310, the 1st substrate that constitutes the aforementioned effect utmost point preferably uses the material that has concurrently through the optical characteristics of sunlight and can stand the thermal property (thermal endurance) that produces when being subjected to laser.Can make sunlight fully arrive the duplexer that is accommodated in the basket by having through the optical characteristics of sunlight.And, be subjected to the situations such as warpage that thermal impact produces in the time of suppressing because of sealing by having thermal endurance, can keep interelectrode distance, therefore can guarantee the long-time stability of power generation characteristics.

And, in Fig. 5, when representing to seal basket 321, the arrow of duplexer 320 puts on the direction of the power of duplexer 320.Lateral shift takes place in order to be suppressed on the duplexer 320 when in the direction duplexer 320 being applied external force, or, preferably between bottom 323, elastomeric element 326 is set to the utmost point 319 and formation basket 321 according to making duplexer 320 keep flexibility and the mode that firmly fixes seals duplexer 320 at above-below direction.

The relative position skew that being provided with of this elastomeric element 326 can be suppressed upper/lower electrode direction in its face, and can improve for the shape stability of external force and can promote vibration strength, so preferably.

And, adopt following structure in the dye-sensitized solar cell 310:, divide the end that is arranged to be connected to that the other end extends to electric conductor 328,329 outside the basket 321 respectively with the effect utmost point 318 to the utmost point 319 according to inboard by the basket that constitutes by the lid with the 1st substrate 311 and casing 322 and do not contact the mode of the side of duplexer 320.

Constitute according to this, can will be used for connecting the other end of the electric conductor 328,329 of not shown external circuit, freely export to outside the basket, therefore can adapt to the diversified condition that is provided with that cooperates the external circuit system from any position of basket 321.

For the end effect of the being connected in utmost point 318 and the other end extend to the outer electric conductor 328 of basket, owing to be set as the side that does not contact duplexer 320 by basket 321 inside, therefore also can be as shown in Figure 5, between each side of oxide electrode 313, conducting film 314 and the 2nd substrate 315 of a part that constitutes duplexer 320 and electric conductor 328, sandwich elastomeric element 326a.Thus, can not contact the mode of each side of oxide electrode 313, conducting film 314 and the 2nd substrate 315 of a part that constitutes duplexer 320 according to the inboard of the 1st substrate 311 of the effect utmost point 318 of the lid by forming basket, divide the end that is arranged to be connected to that the other end extends to the outer electric conductor 328,329 of basket 321 respectively with the effect utmost point 318 to the utmost point 319, and can realize being electrically connected of photo-electric conversion element 310 and outside.

Particularly, in photo-electric conversion element 310, the electric conductor 328 that one end is connected in the effect utmost point 318 is configured to: the face that contact along the end 312a of the elastomeric element 326a and the nesa coating 312 of the formation effect utmost point 318 extends, and wherein elastomeric element 326a is located between each side and electric conductor 328 of oxide electrode 313, conducting film 314 and the 2nd substrate 315 of a part of formation duplexer 320.This configuration can prevent electric conductor 328 short circuit with the contacts side surfaces of the oxide electrode 313 of being located at a part that constitutes duplexer 320 and conducting film 314.And, even when sealing elastomeric element 326a shrinks under the situation of its change of shape, electric conductor 328 can not pass through among the elastomeric element 326a yet, and is present in the end 312a of nesa coating 312 and the contact-making surface of elastomeric element 326a, therefore can be subjected to its big influence hardly.Therefore, because an end of electric conductor 328 keeps stabilizer pole with being electrically connected of nesa coating 312 of the formation effect utmost point 318, so the improvement of this electrical connection can bring the long-time stability of the output characteristic of photo-electric conversion element.

And, in photo-electric conversion element 310, be configured to side 320t with the sidepiece 324 contact duplexers 320 of basket.By such formation the structure in space is not set in the side of duplexer 320, the effect utmost point 318 not only its central portion and near the end also certain keep with to the utmost point 319 state of contact.So in when sealing, the effect utmost point 318 can not be subjected to unbalanced pressure near the end, therefore the 1st substrate 311 grades of the formation effect utmost point 318 can be deformed or damaged possibility suppresses very lowly.

Basket is the best with the form of whole sides of being configured to contact duplexer, yet, also can constitute following mode as described above, promptly only at the thickness direction place of the electric conductor 328 guiding duplexers 320 that an end are connected in the effect utmost point 318, between each side of the sidepiece 324 of basket and oxide electrode 313, conducting film 314 and the 2nd substrate 315 of a part that constitutes duplexer 320, dispose elastomeric element 346a.The parts that have insulating properties by use can be avoided the short circuit of duplexer 320 and electric conductor 328 as elastomeric element 346a, so preferred.If only be configured to have electric conductor 328 near elastomeric element 346a be set and contact between other sidepiece 324 of basket and the duplexer 320, then can obtain above-mentioned roughly same effect.

The manufacture method of the photo-electric conversion element of the 2nd execution mode of the present invention, be dispose have the effect utmost point 318 that carries the oxide semiconductor porous layer 313 of holding sensitizing coloring matter from the teeth outwards, oxide semiconductor porous layer 313 side and its subtend of this effect utmost point 318 dispose to the utmost point 319 and be configured in the manufacture method of photo-electric conversion element 310 of the dielectric substrate 316 of at least a portion between above-mentioned the two poles of the earth 318,319, have following at least two operations.

In the 1st operation, aqueous or gelatinous electrolyte is filled in the oxide semiconductor porous layer 318 of the formation effect utmost point 318 and forms dielectric substrate 316.

In the 2nd operation, be provided with the utmost point 319 and make the i.e. inner face of bottom 323 of its inner bottom surface that contacts the casing 322 that constitutes basket directly or indirectly, and according to making dielectric substrate 316 contact this forms duplexer 318 to the mode overlap action utmost point 318 of the utmost point 319, after the 1st substrate 311 that constitutes this effect utmost point 318 is configured according to the mode of the lid that forms basket, seal with laser method or mull technique the 1st substrate 311 of the formation effect utmost point 318 and casing 322 sidepiece 324 contact site and make basket.

According to above-mentioned the 1st operation, can not after sealing, but inject aqueous or gelatinous electrolyte by being pre-charged with.That is to say, problem during injection electrolyte in the manufacture method in the past, promptly must be after forming cell shapes in that two plate electrode plates are carried out heat bonding, inject through the inlet of offering in advance and between two plate electrodes of delimiting extremely narrow space, on inlet, add loam cake at last, thus the problem that causes manufacturing process to become numerous and diverse; If or the viscosity height of electrolyte, the then problem of essential many times and time in order to inject electrolyte; And the problem that causes the increase manufacturing cost by above-mentioned reason, all the 1st operation by the 2nd execution mode of the present invention is solved.

According to above-mentioned the 2nd operation, make basket owing to seal the 1st substrate 311 of the formation effect utmost point 318 by laser method or mull technique with the contact site of the sidepiece 324 of casing 322, the conduction of the heat that applies in the time of therefore can further being suppressed at sealing and to being adsorbed in the influence of the pigment on the dye-sensitized semi-conducting electrode 313.

Below be that example illustrates each suitable component parts with aforementioned photo-electric conversion element 310.

The plate that material constituted that the 1st substrate 311 of the 2nd execution mode of the present invention uses by light transmission, as glass, PETG, PEN, Merlon, polyether sulphur etc., so long as the general material that uses as the transparency carrier of solar cell just can use.As long as consider to select aptly for the tolerance of electrolyte etc., still consider its purposes, it is good selecting the high substrate of light transmission as far as possible.

Preferably on the face of dye-sensitized semi-conducting electrode 313 sides of the 1st substrate 311, form in advance and have the nesa coating 312 of metal, carbon, conductive metal oxide layer etc., and give conductivity.Forming under metal level or the situation of carbon-coating, be preferably formed as the structure that undermines the transparency for not obvious,, selecting the kind of metal aptly from forming the viewpoint of the film that can not undermine the conductivity and the transparency as nesa coating 312.Can use for example ITO, SnO ₂, mix the SnO of fluorine ₂Deng as conductive metal oxide.

, on the transparency conducting layer 302 on the 1st substrate 311, and then be provided with and make the multichip semiconductor pore membrane carry the dye-sensitized semi-conducting electrode 313 of holding sensitizing coloring matter and forming in mounting.With the 1st substrate 311, transparency conducting layer 302 and the dye-sensitized semi-conducting electrode 313 formation effect utmost points (the window utmost point) 318.The semiconductor that forms the multichip semiconductor pore membrane of dye-sensitized semi-conducting electrode 313 is not particularly limited, so long as be generally used in the material of the porous semi-conductor that forms used for solar batteries, can use, and for example can use TiO ₂, SnO ₂, WO ₃, ZnO, Nb ₂O ₅Deng.But the method illustration that forms perforated membrane is removed the unnecessary method that becomes to grade after the mixture of the formation film based on sol-gal process, atomic swimming electro-deposition, the porous based on blowing agent, coating and polymer particles etc. is arranged, and still is not limited in this.

Owing to need not have light transmission especially, therefore can use metallic plate as the 2nd substrate 315, also can use and the 1st substrate 311 identical materials.Use is provided with the electrode conduct of conducting film 314 to the utmost point 319 on the 2nd substrate 315.Conducting film 314 can use the heat treatment behind for example evaporation, sputter, the coating chlorination platinic acid and the layer of the carbon that forms or platinum etc. so long as have electrode function, is not particularly limited.

At the above-mentioned effect utmost point 318 and between dielectric substrate 316 is set and forms battery component parts with duplexer 320 to the utmost point 319.As described later, the duplexer 320 of the 2nd execution mode of the present invention forms by the following method: aqueous or gelatinous electrolyte is filled in the oxide semiconductor porous layer 313 of the formation effect utmost point 318 and forms after the dielectric substrate 316, after making dielectric substrate 316 form duplexer 320 with the mode overlap action utmost point 318 that the utmost point 319 is contacted, with the direction imposed load of duplexer 320 Surface Vertical.

Therefore, the dielectric substrate 316 of the 2nd execution mode of the present invention also can use the high material of viscosity that in the past was difficult to inject from inlet narrow electrode gap, therefore, can utilize the suitable gelating agent of use and electrolyte has been carried out gelation (plan solidification) and full-bodied material, employed in the past any material all can.

The duplexer 320 that forms with the utmost point 319 is clipped dielectric substrate 316 with the effect utmost point 318 is accommodated in the basket that is made of casing 322 and the lid with the 1st substrate 311, and the inner face of the bottom 323 of the following and casing 322 that constitutes basket of duplexer 320 directly or indirectly contacts.In the basket, the 1st substrate 311 of lid, i.e. the formation effect utmost point 318 is made of the material that has through the optical characteristics of sunlight as mentioned above at least, for example can enumerate the material of transparent and tool rigidity such as propylene, Merlon, polyvinyl chloride, soda-lime glass.The other parts of basket, i.e. the casing 322 that is made of bottom 323 and sidepiece 324 as long as can guarantee and the insulating properties of the electric conductor 328,329 of the external circuit that extends to basket from two electrodes respectively, does not then limit its material especially.

For example the inner bottom surface with the casing 322 that constitutes basket directly contacts and is provided with the utmost point 319, according to making dielectric substrate 316 contact form duplexer 320 to the mode overlap action utmost point 318 of the utmost point 319, and dispose the lid promptly after the 1st substrate 311 that constitutes basket 322 according to the mode of the covering effect utmost point 318, seal the only connecting portion of this lid and basket 322 with laser radiation.Thus, can be as Sealing Method in the past be that duplexer applies loads such as heating or pressurization for battery itself, and the duplexer that will form battery is accommodated in the casing that constitutes basket, and Integratively sealing basket, thereby can obtain dye-sensitized solar cell 310.Also can elastomeric element be set at the inner bottom surface of casing 322 and between to the utmost point 319, and be configured to make the inner bottom surface of casing 322 with to the utmost point 319 indirect contacts.And, also can replace the method that laser radiation seals and use binding agent to seal.

Form the electrolyte of dielectric substrate 316, can be by dripping after the effect utmost point (the window utmost point) 318, with the utmost point 319 is folded incompatible filling, therefore can save in the prior art perforate on to the utmost point 319, inject electrolyte, clog numerous and diverse operation such as hole, so can simple manufacturing process and can realize the reduction labour, so can obtain photo-electric conversion element cheaply.

(the 3rd execution mode)

Followingly describe the 3rd execution mode of the present invention in detail according to embodiment.

Fig. 6 represents that an example of the photo-electric conversion element of the 3rd execution mode of the present invention is the vertical view of dye-sensitized solar cell, and Fig. 7 is the cutaway view of A among Fig. 6-A line.

This dye-sensitized solar cell 401 seals a plurality of duplexers 402 and forms with the state that is arranged in the plane in the basket 403.

Aforementioned duplexer 402 be by a face be provided with oxide semiconductor porous layer 421a the effect utmost point 421 and with this oxide semiconductor porous layer 421a subtend configuration to the utmost point 422, form with the state overlaid that sandwiches dielectric substrate (omit and illustrate) at the above-mentioned effect utmost point 421 and between the utmost point 422.

The aforementioned effect utmost point 421 has: transparency carrier 421b such as glass substrate, light transmission plastic film, be located at tin-doped indium oxide (ITO), fluorine doped tin oxide nesa coating 421c such as (FTO) on this transparency carrier 421b, be located at the oxide semiconductor porous layer 421a on the nesa coating 421c.

Aforementioned oxide semiconductor porous layer 421a is by at titanium oxide (TiO ₂), zinc oxide (ZnO), tin oxide (SnO ₂), niobium oxide (Nb ₂O ₅) surface of waiting the oxide semiconductor particle, the sensitizing coloring matters such as ruthenium complex that absorption has dentates such as second bipyridine, terpyridyl constitute.

And, are conductive boards to the utmost point 422, on substrate 422a such as glass substrate, be formed with the conducting film 422b of the film that is constituted by metals such as paper tinsel or carbon etc.

Be clipped in the aforementioned effect utmost point 421 and to the dielectric substrate between the utmost point 422 (omit diagram), by electrolyte ingredients such as iodine, iodide ion, tert .-butylpyridine being dissolved in the electrolyte that organic solvents such as ethylene carbonate or methoxyacetonitrile form, or in aforementioned electrolyte, adding and poly-ly fluoridize inferior ethene, polyethylene oxygen support derivative, amino acid derivativges etc. and the gel-like electrolyte of gelation etc. constitute as gelating agent.

Constitute the electrolyte of dielectric substrate or the space part that gelatinous electrolytical major part is soaked the oxide semiconductor porous layer that is contained in the effect utmost point 421.By like this, the surface of oxide semiconductor porous layer 421a forms the state by electrolyte or the lining of gelatinous electrolyte.

And, constitute the electrolyte of dielectric substrate or gelatinous electrolyte and can not overflow because of the capillarity in the atomic interparticle space of oxide semiconductor that constitutes oxide semiconductor porous layer 421a peripheral part from duplexer 402.

For this duplexer 402,, then can produce electromotive force at the effect utmost point 421 and between to the utmost point 422 if inject light such as sunlight from transparency carrier 421b side.

Peripheral part at the aforementioned effect utmost point 421 is provided with current collection wiring part 405.The conduction that this current collection wiring part 405 contains electroconductive powder by coating on transparency carrier 421b is stuck with paste and is given drying and the films that metal constituted such as conducting film, paper tinsel or carbon that form, the institutes such as distribution that utilize soldering to form constitute, and be electrically connected on nesa coating 421c.

By this current collection wiring part 405, duplexer 402 and the outside terminal for connecting (omit diagram) of being located at basket 403 can be electrically connected.

In the duplexer 402 of adjacency, insulating properties materials such as elastomeric element 441 described later are being set between adjacent nesa coating 421c or the current collection wiring part 405, between the duplexer 402 of adjacency, can not be electrically connected mutually between the above-mentioned nesa coating 421c or between each current collection wiring part 405.

The basket 403 of taking in aforementioned duplexer 402 has the framework 432 of backboard 431 that is made of plastic flat boards such as metallic plates such as stainless steel or plastics etc. and the peripheral part of being located at this backboard 431.

Framework 432 have the peripheral part of crossing over backboard 431 region-wide and with the backboard 431 prominent side wall portion 432a that establishes and be configured to the window frame portion 432b of subtend slightly vertically in backboard 431.The aforementioned window frame 432b of portion extends and forms one with side wall portion 432a from the upper end of side wall portion 432a towards duplexer 402 sides, for example can use plastic materials such as the material of the metallic plate bending and forming of stainless steel etc. or plastics.

Constitute the side wall portion 432a of aforementioned framework 432 and the peripheral part of backboard 431, bond removably by strippable binding agent such as epoxy resin binding agent, fixing.For example have the instrument of hard and sharp keen leading section, and aforementioned binding agent is peeled off, backboard 431 is separated with side wall portion 432a by inserting with the adhesive segment of side wall portion 432a at backboard 431.

On the aforementioned backboard 431 the laminar elastomeric element 441 that is made of polyurethane, polyethylene, cellular rubber etc. is being set.On this elastomeric element 441, a plurality of duplexers 402 alignment arrangements two-dimensionally become to interconnect shape.At this, the boundary line between the duplexer 402 is represented in the double dot dash line among Fig. 6.

The effect utmost point 421 of above-mentioned duplexer 402 is provided with towards the top, and oxide semiconductor porous layer 421a absorbs light such as the sunlight injected from the 432b of window frame portion top and produce electromotive force.

The transparency carrier 421b of the effect utmost point 421 of this duplexer 402 constitutes the sensitive surface 411 of dye-sensitized solar cell 401.

And, gap filling materials 422 such as aforementioned elastomeric element 441 or silicone oil etc. also can be set so that can not produce the gap between side wall portion 432a and the duplexer 402.

The 432b of window frame portion that constitutes aforementioned framework 432 have from the upper end of side wall portion 432a towards the 432c of frame portion that duplexer 402 sides are extended and be connected in the 432c of frame portion the 432d of stack portion.The 432c of frame portion is arranged on the corresponding zone, position with the current collection wiring part 405 that is connected side wall portion 432a.And the middle stack 432d of portion is arranged near the corresponding zone, position of the current collection wiring part 405 the boundary with the duplexer 402 of adjacency.

As an example, in Fig. 6, the dye-sensitized solar cell 401 shown in Figure 7, rectangular-shaped duplexer 402 with the state that is provided with current collection wiring part 405 at its peripheral part seamlessly two-dimensional arrangement on rectangular-shaped backboard 431.With the corresponding zone, position of the current collection wiring part 405 of the peripheral part that is arranged at this duplexer 402, the middle stack 432d of portion is connected with the 432c in frame portion with rectangular.

Constitute peristome 432e by 432c of frame portion that constitutes the 432b of window frame portion and the middle stack 432d of portion institute area surrounded, this peristome 432e is arranged on the corresponding zone, position with the oxide semiconductor porous layer 421a of the effect utmost point 421 of duplexer 402.

Therefore, in the transparency carrier 421b of the effect utmost point 421, become the state that exposes laterally by the peristome 432e of the 432b of window frame portion corresponding to the zone of the position of oxide semiconductor porous layer 421a.

And the aforementioned window frame 432b of portion is connected to a plurality of duplexers 402 that are configured on the backboard 431, and duplexer 402 is pushed towards backboard 431 by this 432b of window frame portion.

And the contact-making surface of the effect utmost point 421 of 432b of window frame portion and duplexer 402 can be provided with sealing materials such as O type circle.By the sealing material is set, can improve the sealing of the effect utmost point 421 of 432b of window frame portion and duplexer 402.

Following illustration is sealed in a plurality of duplexers 402 in the basket 403 and forms the method for dye-sensitized solar cell 401.

Preparation be provided with the effect utmost point 421 of oxide semiconductor porous layer 421a with to the utmost point 422.This effect utmost point 421 can be made with well-known method, for example can be after being formed on nesa coating 421c on the transparency carrier 421b by sputtering method etc., will contain the atomic paste of oxide semiconductor and coat and carry out heat treated on the nesa coating 421c and make.

Thereby, form current collection wiring part 405 at the peripheral part of the effect utmost point 421.

Electrolyte or gel-like electrolyte are dripped, coat the oxide semiconductor porous layer 421a surface of the aforementioned effect utmost point 421 or the surface of the utmost point 422 is provided with.To act on the utmost point 421 then with overlapping and form duplexer 402 with the state that clips electrolyte or gel-like electrolyte betwixt to the utmost point 422.

Elastomeric element 441 is set on backboard 431, on this elastomeric element 441, the utmost point 422 is disposed a plurality of duplexers 402 towards the state of elastomeric element 441 according to making.Lead (omit diagram) is waited and the utmost point 422 is electrically connected, and this lead is electrically connected to the outside terminal for connecting (omission illustrates) that is located at basket 403.

And, also gap filling material 442 can be arranged on and corresponding zone, the position of current collection wiring part 405.

Secondly, preparation has and is being provided with the 432b of window frame portion, and the framework 432 of side wall portion 432a of 432c of frame portion and the middle stack 432d of portion with corresponding zone, the position of current collection wiring part 405, so that the 432b of window frame portion of framework 432 is connected to the effect utmost point 421 and the state that utilizes the 432b of window frame portion that duplexer 402 is pushed towards backboard 431 directions, utilize that strippable binding agent bonds removably, the peripheral part of fixed frame 432 and backboard 431.

Pressing force by the 432b of this window frame portion, make electrolyte or gelatinous electrolyte powder be distributed in the effect utmost point 421 and all surfaces to the utmost point 422, and electrolyte or gelatinous electrolyte powder are distributed in the interior oxidation thing semiconductor surface of the porous of the oxide semiconductor porous layer 421a that acts on the utmost point 421.

The size of adjusting framework 432 in advance is seamlessly being sealed in duplexer 402 in the basket 403, the state of duplexer 402 to be pushed by the 432b of window frame portion toward back plate 431 directions of framework 432 is in the full sealing seamlessly on every side of the side wall portion 432a of framework 432.

According to this example, the 432b of window frame portion has: be arranged on the 432c of frame portion in the corresponding zone, position of the current collection wiring part 405 that is connected side wall portion 432a and be arranged near the middle stack 432d of portion in the corresponding zone, position of the current collection wiring part 405 the boundary with the duplexer 402 of adjacency, thus, can under the state that the oxide semiconductor porous layer 421a that makes the effect utmost point 421 by the peristome 432e that is surrounded by this 432c of frame portion and the middle stack 432d of portion exposes laterally, utilize 432c of frame portion and the middle stack 432d of portion that each duplexer 402 is pushed towards backboard 431 directions.

The 432b of window frame portion be connected to and be arranged on each duplexer 402 peripheral part current collection wiring part 405 corresponding zone, position and duplexer 402 pushed towards backboard 431, so pressing force will be being that the center applies near the peripheral part of duplexer 402.

Therefore, no matter the allocation position of duplexer 402 is near the peripheral part of backboard 431 or near the central authorities of backboard 431, the pressing force that all can will put on each duplexer 402 is set as roughly certain.The effect utmost point 421 and roughly certain can be on whole of the sensitive surface 411 of dye-sensitized solar cell 401, made thus, the uneven of generating efficiency can be suppressed the distance between the utmost point 422.

And, in the 432b of window frame portion, the 432d of stack portion on the 432c of frame portion, being connected with, thereby make the 432b of window frame portion have excellent transverse strength, ratio is in the past with the difficult warpage of the tabular lid of weight, can suppress change, can suppress to act in each duplexer 402 utmost point 421 and, can obtain roughly certain generating efficiency the distance change between the utmost point 422 because of the pressing force that distortion caused of the 432b of this window frame portion.

In the 3rd execution mode of the present invention, push duplexer 402 with the 432b of window frame portion toward back plate 431 directions, and will act on the utmost point 421 with overlapping with the state that clips electrolyte or gel-like electrolyte betwixt to the utmost point 422, and pushing under the state of duplexer 402 towards backboard 431 directions with the 432b of window frame portion, the peripheral part of fixed frame 432 and backboard 431, thus duplexer 402 Integrativelies can be sealed in the basket 403.

And, as explained above, the 432b of window frame portion is located at the corresponding zone, position with the current collection wiring part 405 that does not participate in generating electricity, and the oxide semiconductor porous layer 421a of the effect utmost point 421 exposed laterally, thereby can increase area ratio, can more effectively utilize the sensitive surface 411 of dye-sensitized solar cell 401 for oxide semiconductor porous layer (hatched example areas among Fig. 7) 421a of the sensitive surface 411 of dye-sensitized solar cell 401.

And, by peristome 432e the oxide semiconductor porous layer 421a of the effect utmost point 421 exposed laterally by the 432b of window frame portion, light such as sunlight directly can be injected the effect utmost point 421 and oxide semiconductor porous layer 421a absorbed.

So the formation of injecting the effect utmost point with light through lid is different, before light was injected the effect utmost point 421, luminous intensity can not reduce, and can further improve generating efficiency.

And, by the 432b of window frame portion is arranged on and corresponding zone, the position of current collection wiring part 405, can makes the light of sunlight etc. can not inject current collection wiring part 405 and can suppress and rise because of the temperature of the current collection wiring part 405 that irradiates light caused.

Generally speaking, current collection wiring part 405 is formed with coating conduction and sticks with paste and give drying and the conducting film that forms, the film that is made of metals such as paper tinsel or carbon, the distribution that forms by soldering etc. on substrates such as transparency carrier.In case so current collection wiring part 405 temperature that constitute rise, then because of with the difference of the thermal coefficient of expansion of substrate can with the near interface generation thermal stress of substrate, have situation from strippable substrate.

Therefore, rise, can suppress to make current collection wiring part 405 from strippable substrate, can obtain excellent long-time stability owing to temperature rises by the temperature that suppresses current collection wiring part 405.

And, by between backboard 431 and duplexer 402, elastomeric element 441 being set, the lateral shift that can when the pressing force that duplexer 402 is pushed towards backboard 431 directions puts on duplexer 402, suppress duplexer 402, and, can be while making duplexer 402 keep flexibility duplexer 402 to be sealed in the basket 403 with the state that fixedly secures at above-below direction

And, by elastomeric element 441 or gap filling material 442 are set, can the inhibitory action utmost point 421 and relative position relation direction skew in face to the utmost point 422, and can obtain shape stability and vibration strength for the excellence of external force.

And the side wall portion 432a that constitutes framework 432 bonds removably, fixes by strippable binding agent with the peripheral part of backboard 431, thus, can peel off binding agent and side wall portion 432a is separated with backboard 431.Therefore, can after separate side wall portion 432a and backboard 431, take out each duplexer 402 from backboard 431, thereby can carry out the replacing of duplexer 402 or the utilization again of backboard 431 and framework 432.

And the technical scope of the 3rd execution mode of the present invention is not to be defined in above-mentioned execution mode, can carry out various changes in the scope of the purport that does not break away from the 3rd execution mode of the present invention.

For example, side wall portion 432a and backboard 431 also can utilize screw etc. to fix removably.

And, but also side wall portion 432a and the 432b of window frame portion do not form one and make the 432b of window frame portion can be dismantled and assembled with respect to side wall portion 432a.Like this, can with side wall portion 432a with after the 432b of window frame portion separates, similarly take out each duplexer 402 with present embodiment, thereby can carry out the replacing of duplexer 402 or the utilization again of backboard 431 and framework 432 from backboard 431.

For example with present embodiment similarly, make side wall portion 432a and the 432b of window frame portion fixing removably by using strippable binding agent or screw etc.And, by using elastic claw 406 latch for printed circuit such as grade as shown in Figure 8, use the flap (flap) 407 be provided with engaging parts such as engaging pawl etc. as shown in Figure 9, and can make the 432b of window frame portion fixing removably with respect to side wall portion 432a.

Fig. 8 is other example of the photo-electric conversion element of the 3rd execution mode of the present invention, is the end 432f of the upper face side of a plurality of elastic claws 406 the being located at side wall portion 432a cutaway view as the dye-sensitized solar cell of latch for printed circuit.

Aforementioned a plurality of elastic claw 406 is based in the end 432f of the upper face side of side wall portion 432a, if the 432b of window frame portion is pressed into the inner space 461 that is surrounded with above-mentioned a plurality of elastic claws 406, then make it to broaden, and the 432b of window frame portion can be inserted towards the duplexer in being disposed at side wall portion 432a 402 pushing open between a plurality of elastic claws 406.

Aforementioned elastic claw 406 is made for synthetic resin such as plastics, forms one with side wall portion 432a, protrude in from the side of the outstanding front end of side wall portion 432a, and formation is sticked in the shape of the 432c of frame portion of the 432b of window frame portion.Be formed on inclined plane 462 from the outstanding front end of the side wall portion of this elastic claw 406 in order to realize that the 432b of window frame portion is pressed into the space 461 that is surrounded by a plurality of elastic claws 406, or realize glidingly utilizing this to be pressed into and the pushing open of a plurality of elastic claws 406 of causing, in order to accept the 432b of window frame portion glidingly, space 461 is constituted the shape that expands into taper.

By space 461, cross front end pawl 463 towards the 432b of window frame portion that duplexer 402 is pressed into, and than front end pawl 463 more after duplexer 402 side shiftings, then the front end pawl 463 of elastic claw 406 with regard to the elastic restoring force of utilizing elastic claw 406 and be sticked in the 432b of window frame portion framework 432c above.

At this moment, elastic claw 406 is with state that the 432b of window frame portion is pushed towards duplexer 402 and realize function that the 432b of window frame portion is kept removably.

Fig. 9 is another other example of the photo-electric conversion element of the 3rd execution mode of the present invention, for be provided with the cutaway view of the dye-sensitized solar cell of flap 407 on the end 432f of the upper face side of side wall portion 432a with rotating freely.

Mentioned hinge plate 407 is arranged at the end 432f of the upper face side of side wall portion 432a with rotating freely, and section L word shape that can be by the 432c of frame portion on being arranged on engaging parts such as engaging pawl 471 on this flap 407 and being arranged on the 432b of window frame portion be stuck engaging of parts 409, and keep the 432b of window frame portion removably with the state that the 432b of window frame portion is pushed to duplexer 402.

Mentioned hinge plate 407 is plastic integrally formed product, have with the end 432f of the upper face side of side wall portion 432a roughly with wide plate body 472, and the front end of this plate body 472 with respect to plate body 472 vertically prominent establish engage engaging part such as pawl 471, its section shape is the L word shape.

Aforementioned plate body 472 quilts support along the cylindric axial region axle of the end 432f setting of the upper face side of side wall portion 432a, and flap 407 can be the center rotation with the axial region.

And the parts 408 that are stuck that are based in the 432c of frame portion of the 432b of window frame portion have that outstanding the prolonging of peripheral part above the 432c of frame portion portion 481, and to prolong side of the outstanding front end that portion 481 from this outstanding and be sticked in the rectangular-shaped front end pawl 482 of section of the engaging pawl 471 of flap 407.This is stuck the top peripheral part Zone Full of the parts 408 leap frame 432c of portion and is provided with.

If towards the 432b of the window frame portion rotary gemel plate 407 that is located on the duplexer 402, then engaging pawl 471 front ends of flap 407 can butt the window frame 432b of portion the 432c of frame portion and on one side the 432b of window frame portion is pushed towards backboard 431 directions, on one side move towards the parts 408 that are stuck of the 432b of window frame portion.

If the engaging pawl 471 of flap 407 engages with the parts 408 that are stuck of the 432b of window frame portion, then the 432b of window frame portion just keeps with the state of being pushed towards duplexer 402 removably by the engaging pawl 471 of flap 407.

By window frame portion being arranged on and corresponding zone, the position of current collection wiring part, can under the state that exposes outside the oxide semiconductor porous course that makes the effect utmost point by peristome, utilize window frame portion that each duplexer is pushed towards the backboard direction.Since window frame portion be connected to and be arranged on each duplexer peripheral part the current collection wiring part corresponding zone, position and duplexer pushed towards the backboard direction, therefore, pressing force is being that the center applies near the peripheral part of each duplexer.

Therefore, can will put on the pressing force of each duplexer be set as roughly necessarily, and on whole of the sensitive surface of dye-sensitized solar cell, make the effect utmost point and the distance between the utmost point roughly be necessarily, can suppress the uneven of generating efficiency.

And, in window frame portion, stack portion in frame portion, being connected with, thereby make window frame portion have excellent transverse strength, ratio is in the past with the difficult warpage of the tabular lid of weight, can suppress change, can suppress to act in each duplexer the utmost point and, can obtain roughly certain generating efficiency the distance change between the utmost point because of the pressing force that distortion caused of this window frame portion.

And, push duplexer with window frame portion toward back plate direction, and will act on the utmost point with overlapping with the state that clips electrolyte or gel-like electrolyte betwixt to the utmost point, and pushing under the state of duplexer towards the backboard direction with window frame portion, the peripheral part of fixed frame and backboard, thus the duplexer Integratively can be sealed in the basket.Therefore, needn't use as in the past with sealant fit the effect utmost point with to the monocell of the utmost point, and can effectively utilize the sensitive surface of dye-sensitized solar cell.

And, by peristome the oxide semiconductor porous course outside of the effect utmost point is exposed by window frame portion, energy increases the area ratio for the oxide semiconductor porous layer of the sensitive surface of dye-sensitized solar cell, can more effectively utilize the sensitive surface of dye-sensitized solar cell.

And, by peristome the oxide semiconductor porous course outside of the effect utmost point is exposed by window frame portion, light such as sunlight directly can be injected the effect utmost point and the oxide semiconductor porous layer is absorbed, the formation of injecting the effect utmost point with light through lid is different, luminous intensity can not reduce, and can further improve generating efficiency.

(the 4th execution mode)

The following photo-electric conversion element of having implemented the 4th execution mode of the present invention with reference to accompanying drawing explanation.

Figure 10 is that an example of the photo-electric conversion element of expression the 4th execution mode of the present invention is the general profile chart of dye-sensitized solar cell.Figure 11 is the approximate vertical view of the dye-sensitized solar cell of expression Figure 10.

Among Figure 10 and Figure 11, label 510 for dye-sensitized solar cell, 511 be the 1st substrate, 512 for nesa coating, 513 for the oxide semiconductor porous layer, 514 for the effect utmost point, 515 for dielectric substrate, 516 be the 2nd substrate, 517 for conducting film, 518 for the utmost point, 519 is adhesive layer for adhesive layer, 534 for lid, 533 for framework, 532 for basket, 531 for duplexer, 530 for gap filling material, 525 for electric conductor, 521 for elastomeric element, 520.

This dye-sensitized solar cell 510 is roughly by constituting with the lower part: a face 514a is provided with the effect utmost point 514 that makes sensitizing coloring matter be supported at the oxide semiconductor porous layer 513 on surface, with the configuration of face 514a subtend to the utmost point 518, be formed at a face 514a and to the dielectric substrate 515 of subtend between the face 518a of a face 514a (to call " to a face 518a of the utmost point 518 " in the following text) of the utmost point 518, be located at the electric conductor 520 of the circumference of a face 514a, and the basket 530 of taking in above-mentioned parts.

And in this dye-sensitized solar cell 510, the electrolytical major part that forms dielectric substrate 515 is to soak the state of the gap that is contained in oxide semiconductor porous layer 513.

The effect utmost point 514 has the 1st substrate 511 and order forms on one face 511a nesa coating 512 and oxide semiconductor porous layer 513.And, at the circumference of a face 514a of the effect utmost point 514, electric conductor 520 is being set according to the mode of the side 513a that surrounds oxide semiconductor porous layer 513.

The utmost point 518 is had the 2nd substrate 516 and is formed at conducting film 517 on the one face 516a.

In the dye-sensitized solar cell 510, to act on the utmost point 514 and the utmost point 518 is clipped dielectric substrate 515 formed duplexers 525 as photo-electric conversion element performance function.

In dye-sensitized solar cell 510, duplexer 525 is accommodated in the basket 530, and this basket 530 has: coat the side 525a of duplexer 525 and the effect utmost point 514 another face 514b a part framework 531, and contact another face 518b of the utmost point 518 is fixed in duplexer 525 lid 532 of framework 531.

Framework 531 has: the 531A of frame portion in whole zone that coats the side 525a of duplexer 525 from the outside; And from the 531A of frame portion perpendicular to this frame portion and (center position) prominent press section 531B that establishes to the inside.And make duplexer 525 the 531A of side 525a connecting frame portion inner face 531a or the side 525a of duplexer 525 is disposed near the inner face 531a of the 531A of frame portion and duplexer 525 is accommodated in the basket 530.And another face 514b of the effect utmost point 514 joins with the inner face 531b of press section 531B by adhesive layer 533.And, press section 531B is set as the zone of covering corresponding to the position that is formed on the electric conductor 520 on the above-mentioned face 514a on another face 514b of the effect utmost point 514, the side 520a of oxide semiconductor porous layer 513 side of the end face 531c of press section 531B and electric conductor 520 is present in roughly with on the one side.

And lid 532 is by elastomeric element 519 and join with another face 518b to the utmost point 518.And lid 532 is fixed in framework 531 by adhesive layer 534.

And, press section 531B is set as the structure of covering corresponding to the zone of the position that is formed on the electric conductor 520 on the above-mentioned face 514a on another face 514b of the effect utmost point 514, as shown in figure 10, the side 520a that is not only oxide semiconductor porous layer 513 side of the end face 531c of press section 531B and electric conductor 520 is present in roughly the structure with one side, and the end face 531c that comprises press section 531B is present in the structure in oxide semiconductor porous layer 513 existing zone, or the end face 531c of press section 531B is present in the structure that more relies on the zone of the 531A of frame portion side than the side 520a of electric conductor 520.

And, between lid 532 and electric conductor 520,, and dispose gap filling material 521 in the mode of surrounding to the side of the utmost point 518 by elastomeric element 519.And the photo-electric conversion element of the 4th execution mode of the present invention can not be provided with gap filling material.

Structure thus, duplexer 525 top and below by the press section 531B of

framework

531 and 532 double teams of lid, and under the state that the direction of edge and the Surface Vertical of this duplexer is pressed, be accommodated in the basket 530.And the region-wide of the side 525a of duplexer 525 covered by the 531A of frame portion under this state, and duplexer 525 utilizes basket 530 and sealed by Integratively.

And lid 532 is fixed in framework 531 by adhesive layer 534, but preferably can pass through to insert between framework 531 and lid 532 thin, the hard cutters such as blade of razor, and lid 532 is taken out from framework 531 easily.And, lid 532 fixedly be not limited to the bonding, carry out and also can be screwed.

The 1st substrate 511 uses the substrate that translucent material constituted, as glass, PETG, PEN, Merlon, polyether sulphur etc., so long as the general material that uses as the transparency carrier of solar cell just can use.The 1st substrate 511 considers for the tolerance of electrolyte etc. and selects aptly get final product that still consider its purposes, it is good selecting the high substrate of light transmission as far as possible.

Nesa coating 512 is in order to give the 1st substrate 511 conductivity, and is formed at the film that is made of metal, carbon, conductive metal oxide etc. of one face 511a.

Form under metallic film or the situation of carbon film, be set as the not obvious structure that undermines the transparency of the 1st substrate 511 as nesa coating 512.The conductive metal oxide that forms nesa coating 512 can use for example indium tin oxide (Indium-Tin Oxide, ITO), tin oxide (SnO ₂), mix the tin oxide of fluorine etc.

Oxide semiconductor porous layer 513 is located on the nesa coating 512, and its surface is carried and held sensitizing coloring matter.The semiconductor that forms oxide semiconductor porous layer 513 is not particularly limited, so long as be generally used in the material of the porous semi-conductor that forms used for solar batteries, can use.Above-mentioned semiconductor for example can use titanium oxide (TiO ₂), tin oxide (SnO ₂), tungsten oxide (WO ₃), zinc oxide (ZnO), niobium oxide (Nb ₂O ₅) etc.

As the method that forms oxide semiconductor porous layer 513, but illustration is removed the unnecessary method that becomes to grade after the mixture of the formation film based on sol-gal process, atomic swimming electro-deposition, the porous based on blowing agent, coating and polymer particles etc. is arranged, but is not limited in this.

As sensitizing coloring matter, can use the organic pigments such as containing metal complex compounds such as ruthenium complex, porphyrin, phthalocyanine dye, eosin, rhodamine, part cyanines etc. that second bipyridine structure, terpyridyl structure etc. are contained in dentate, be not particularly limited aspect purposes, the use, and can selecting to have the material that is suitable for semi-conductive drive characteristic.

Dielectric substrate 515 soaks electrolyte to be contained in the oxide semiconductor porous layer 513 and forms, or after electrolyte being soaked be contained in the oxide semiconductor porous layer 513, use suitable gelating agent and make electrolyte gelation (imitative cure) and integrally formed with oxide semiconductor porous layer 513.

As electrolyte, use is dissolved in electrolyte ingredients such as iodine, iodide ion, tert .-butylpyridine the electrolyte that organic solvents such as ethylene carbonate or methoxyacetonitrile form.

Employed gelating agent as with the electrolyte gelation time can be enumerated poly-inferior ethene, polyethylene oxygen support derivative, the amino acid derivativges etc. fluoridized.

As the 2nd substrate 516, can use and the 1st substrate 511 identical materials, or can use metallic plate, synthetic resin board etc. owing to do not need to have light transmission especially.

Conducting film 517 is in order to give the 2nd substrate 516 conductivity, and the film that is constituted by metals such as paper tinsel, carbon etc. that on one face 516a, forms.Conducting film 517 can use the heat treatment behind for example evaporation, sputter, the coating chlorination platinic acid and the layer of the carbon that forms or platinum etc. as long as possess electrode function, is not particularly limited.

Can use foamed polyethylene, foamed polyurethane, cellular rubber etc. as elastomeric element 519.

In dye-sensitized solar cell 510, by utilizing basket 530 sealing duplexers 525, and apply external force in the direction of the Surface Vertical of duplexer 525 upper edges and this duplexer.By making elastomeric element 519 between between to the utmost point 518 and lid 532, and can be by this external force inhibitory action utmost point 514 and between the utmost point 518 lateral shift taking place.And, by elastomeric element 519, can make duplexer 525 keep being firmly fixed at basket 530 in the flexibility in direction with the Surface Vertical of this duplexer.

As electric conductor 520, can enumerate and utilize silk screen print method, form the type of circuit, or carry out soldering and form the type of circuit with conductivity ink such as silver.Electric conductor 520 is in order to be collected in the electronics that take place in the dye-sensitized solar cell 510 effectively, and is located at the circumference (in order to surround the side of oxide semiconductor porous layer 513) of the effect utmost point 514.

And, by this electric conductor 520, duplexer 525 is electrically connected with the outside terminal for connecting of being located at basket 530 (omitting diagram).

Can use foamed polyethylene, foamed polyurethane, cellular rubber etc. as gap filling material 521.

By making gap filling material 521 between lid 532 and electric conductor 520, the external force that can be produced by with basket 530 sealing duplexers 525 time, the inhibitory action utmost point 514 and between the utmost point 518 lateral shift taking place.And, utilize gap filling material 521, can make duplexer 525 keep being firmly fixed at basket 530 in the flexibility in direction with this duplexer Surface Vertical.

As the framework 531 that forms formation basket 530 and the material of lid 532, be not particularly limited, can use various metals, pottery, various synthetic resin etc.

Binding agent as forming adhesive layer 533 as long as the 1st substrate 511 can be bonded in framework 531, then can use any material, the particularly preferred binding agent that can take out duplexer 525 by applying predetermined external force easily from framework 531.As the binding agent that forms adhesive layer 533, for example can using, epoxy is a binding agent etc.

As the binding agent that forms adhesive layer 534, can use and form the binding agent identical materials of adhesive layer 533, as long as lid 532 can be bonded in framework 531, then can use any material.Particularly, as the binding agent that forms adhesive layer 534, preferably can take out the binding agent of lid 532 easily from framework 531 by applying predetermined external force.As the binding agent that forms adhesive layer 534, for example can using, epoxy is a binding agent etc.

As described above, in dye-sensitized solar cell 510, behind the assembling duplexer 520, do not need electrolyte is filled in the effect utmost point 514 and between the utmost point 518, so can simplify working process.And the sealing material that dye-sensitized solar cell 510 need be made of thermoplastic resin etc. is so that weatherability is a long-term reliability is good.And, the effect utmost point 514 of dye-sensitized solar cell 510 and to not needing to be provided with distance between the utmost point 518, so excellent in power generation efficiency.

And, the press section 531B that is located at the framework 531 that constitutes basket 530 of dye-sensitized solar cell 510, on another face 514b of the effect utmost point 514, cover and be formed on the electric conductor 520 existing zones on the face 514a, the part of the participation generating of the effect utmost point 514 be can't help coverings such as cover plate, and utilizes basket 530 sealing duplexers 525.Therefore, can not reduce owing to inject the light quantity of the part of the participation generating that acts on the utmost point 514, so dye-sensitized solar cell 510 has better generating efficiency.

And, in dye-sensitized solar cell 510, electric conductor 520 is formed at the circumference of a face 514a of the effect utmost point 514, and the area of the part of participation generating that therefore can the increase effect utmost point 514 is so dye-sensitized solar cell 510 has better generating efficiency.

And, in dye-sensitized solar cell 510, duplexer 525 removably is fixed on the framework 531 by adhesive layer 533, and lid 532 removably is fixed on the framework 531 by adhesive layer 534, when duplexer 525 takes place can pull down duplexer from basket 530 and repair or change into qualified product under the bad situation.And, because reusable basket 530, so can also cut down manufacturing cost.

Secondly, one example of manufacture method of the photo-electric conversion element of the 4th execution mode of the present invention is described with reference to Figure 10.

In this example, at first prepare to go up and the effect utmost point 514 that constitutes with the face 511a that preordering method sequentially is formed on nesa coating 512 and oxide semiconductor porous layer 513 the 1st substrate 511.

Then, the circumference at a face 514a who acts on the utmost point 514 is provided with electric conductor 520.

Then, the electrolyte that has added gelating agent in advance dripped and soak be contained in oxide semiconductor porous layer 513 after, make this electrolyte gelation, form the dielectric substrate 515 that constitutes one with oxide semiconductor porous layer 513.

Then, according to the mode that the inner face 531b of the press section 531B that makes effect another face 514b of the utmost point 514 and framework 531 by adhesive layer 533 joins, the configuration effect utmost point 514 in framework 531.

Then, according to making conducting film 517 be overlapped in the mode of dielectric substrate 515, will overlap on the effect utmost point 514 utmost point 518, and will be formed in the framework 531 with the duplexer 525 that the effect utmost point 514 forms with the utmost point 518 is clipped dielectric substrate 515.

Then, according to surrounding the side of the utmost point 518 and the mode that is connected to electric conductor 520 are disposed gap filling material 521.

Then, dispose lid 532 according to the mode that covers the utmost point 518 by elastomeric element 519.

Then, on one side from the outside of lid 532 towards with the direction imposed load of the duplexer Surface Vertical of duplexer 525, by adhesive layer 534 lid 532 is fixed in framework 531 on one side,, thereby obtains dye-sensitized solar cell 510 with basket 530 sealing duplexers 525.

In this embodiment, utilizing the textural different of basket 530 sealing duplexers 525 with above-mentioned the 1st example.Among Figure 12, give same numeral and omit its explanation for the inscape identical with the inscape of the 1st example shown in Figure 10.

In dye-sensitized solar cell 540, the inner face 531a of the side 525a of duplexer 525 and the 531A of frame portion joins, and another face 514b of the effect utmost point 514 joins with the inner face 531b of press section 531B by seal member 541.

And lid 532 joins by seal member 542 and framework 531.And lid 532 utilizes screw 543 to be fixed on the framework 531.

And in order fully to guarantee the sealing of 530 pairs of duplexers 525 of basket, a face 514a who is preferably in the inner face 531b of press section 531B of framework 531 and the effect utmost point 514 go up to be provided with the fitting portion (omitting diagram) that has in order to the ditch of chimeric seal member 541 etc.And, be preferably in the fitting portion (omitting diagram) that has in order to the ditch of chimeric seal member 542 etc. is set on the face that contacts with lid 532 of the 531A of frame portion of framework 531 and lid 532 and the face that the 531A of frame portion contacts.

Seal member 541,542 can use by acrylonitrile-butadiene rubber, silicon rubber, polyurethane rubber, contain O type circle that fluorubber elastomeric material or polytetrafluoroethylene etc. constitute, pad etc.

As screw 543,, can use so long as lid 532 can be engaged, is fixed in framework 531.

And, in this example, as the parts that lid 532 engaged, are fixed in framework 531 and illustration screw 543, but the photo-electric conversion element of the 4th execution mode of the present invention is not limited to this.In the photo-electric conversion element of the 4th execution mode of the present invention, as the parts that lid engaged, are fixed in framework, can use the tabular fastener card of hinge that for example will rotatably be located on the lid to end the parts that sandwich the tightening power of spring of the sleeve-like that is the コ font by the parts of fastener, the section that utilizes mode according to frame portion, press section and the top surface of contact framework to be installed in the basket outside of being located at framework.And, aforementioned fastener is limited to also to be can be by the parts of fastener fitting portion is embedded in by the parts of fitting portion.

By forming this structure, produce under the bad situation at duplexer 525, can easily pull down duplexer 525 and repair, or be replaced by qualified product from basket 530.

The photo-electric conversion element of the 4th execution mode of the present invention after the assembling duplexer, does not need electrolyte is filled in the effect utmost point and between the utmost point, so can simplify working process.And the sealing material that the photo-electric conversion element of the 4th execution mode of the present invention need not be made of thermoplastic resin is so that weatherability is a long-term reliability is good.And, the effect utmost point of the photo-electric conversion element of the 4th execution mode of the present invention and to not needing to be provided with distance between the utmost point, so excellent in power generation efficiency.And, at least the zone that forms electric conductor of the press section covering effect utmost point of being located at the framework that constitutes basket of the photo-electric conversion element of the 4th execution mode of the present invention, the part of the participation generating of the effect utmost point is not with coverings such as cover plates, and the duplexer that forms with the utmost point is clipped dielectric substrate with the effect utmost point with basket sealing, therefore, can not reduce owing to inject the light quantity of the part of the participation generating that acts on the utmost point, therefore have better generating efficiency.

And, in the photo-electric conversion element of the 4th execution mode of the present invention, if electric conductor is formed on the circumference of the effect utmost point, the area of the part of participation generating that then can the increase effect utmost point, can reduce the resistance of substrate, so can realize the photo-electric conversion element that generating efficiency is better.

And, in the photo-electric conversion element of the 4th execution mode of the present invention,, then take place can it be pulled down and repair or be replaced with qualified product from basket under the bad situation at duplexer if it is removably fixing to constitute the framework and the lid of basket.And, because reusable basket, so can cut down manufacturing cost.

And, in the photo-electric conversion element of the 4th execution mode of the present invention,,, also can be suppressed at the effect utmost point and to lateral shift takes place between the utmost point even then apply external force towards direction with the duplexer Surface Vertical if folder is established elastomeric element between to the utmost point and lid.And, by elastomeric element, duplexer can be kept flexibility and is firmly fixed at basket in the direction with this duplexer Surface Vertical.

(the 5th execution mode)

The following photo-electric conversion element of implementing the 5th execution mode of the present invention that illustrates with reference to accompanying drawing.

Figure 13 is that an example of the photo-electric conversion element of expression the 5th execution mode of the present invention is the general profile chart of dye-sensitized solar cell.

Among Figure 13, label 610 be expressed as dye-sensitized solar cell, 611 be the 1st substrate, 612 for nesa coating, 613 for the oxide semiconductor porous layer, 614 for the effect utmost point, 615 for dielectric substrate, 616 be the 2nd substrate, 617 for conducting film, 618 for to the utmost point, 619 for elastomeric element, 620 for duplexer, 630 for basket, 631 for body, 632 for lid, 641 for seal member, 642 for screw.

This dye-sensitized solar cell 610 is roughly by constituting with the lower part: face 614a be provided with the effect utmost point 614 that makes sensitizing coloring matter be supported at the oxide semiconductor porous layer 613 on surface, with a face 614a subtend dispose to the utmost point 618, be formed at a face 614a and to the subtend of the utmost point 618 between the face 618a of a face 614a (to call " to a face 618a of the utmost point 618 " in the following text) dielectric substrate 615 and the basket 630 of taking in above-mentioned parts.

And in this dye-sensitized solar cell 610, the electrolytical major part that forms dielectric substrate 615 is to soak the state of the gap that is contained in oxide semiconductor porous layer 613.

The effect utmost point 614 has the 1st substrate 611 and goes up nesa coating 612 and the oxide semiconductor porous layer 613 that order forms in one face 611a.

The utmost point 618 is had the 2nd substrate 616 and is formed at conducting film 617 on the one face 616a.

In dye-sensitized solar cell 610, can be used as photo-electric conversion element performance function to act on the utmost point 614 and the utmost point 618 is clipped dielectric substrate 615 formed duplexers 620.

In dye-sensitized solar cell 610, duplexer 620 is accommodated in the basket 630, this basket 630 have the side 620a that coats duplexer 620 and to the body 631 of the section concavity of another face 618b of the utmost point 618, and join with another face 614b that acts on the utmost point 614 and duplexer 620 be fixed in the lid 632 of body 631.And body 631 is by elastomeric element 619 and join with another face 618b to the utmost point 618.

And lid 632 joins with body 631 by seal member 641.And lid 632 utilizes screw 642 and is fixed in body 631.

And in order fully to guarantee the sealing of 630 pairs of duplexers 620 of basket, a face 631a that joins with lid 632 that is preferably in body 631 and a face 632a of lid 632 go up the fitting portion (omitting diagram) that has in order to the ditch of chimeric seal member 641 etc. are set.

By forming this structure, duplexer 620 top and below by body 631 and 632 double teams of lid, and be accommodated in the basket 630 with the state that is pressed in direction with the Surface Vertical of this duplexer.And the region-wide of the side 620a of duplexer 620 covered by body 631 under this state, and duplexer 620 is sealed by basket 630 Integrativelies.

The 1st substrate 611 uses the substrate that translucent material constituted, as glass, PETG, PEN, Merlon, polyether sulphur etc., so long as the general material that uses as the transparency carrier of solar cell just can use.The 1st substrate 611 considers for the tolerance of electrolyte etc. and selects aptly get final product that still consider its purposes, it is good selecting the high substrate of light transmission as far as possible.

Nesa coating 612 is in order to give the 1st substrate 611 conductivity, and is formed at the film that is made of metal, carbon, conductive metal oxide etc. of one face 611a.Form under metallic film or the situation of carbon film, be set as the not obvious structure that undermines the transparency of the 1st substrate 611 as nesa coating 612.The conductive metal oxide that forms nesa coating 612 can use for example indium tin oxide (Indium-Tin Oxide, ITO), tin oxide (SnO ₂), mix the tin oxide of fluorine etc.

Oxide semiconductor porous layer 613 is located on the nesa coating 612, and its surface is carried and held sensitizing coloring matter.The semiconductor that forms oxide semiconductor porous layer 613 is not particularly limited, so long as be generally used in the material of the porous semi-conductor that forms used for solar batteries, can use.Above-mentioned semiconductor for example can use titanium oxide (TiO ₂), tin oxide (SnO ₂), tungsten oxide (WO ₃), zinc oxide (ZnO), niobium oxide (Nb ₂O ₆) etc.

As the method that forms oxide semiconductor porous layer 613, but illustration is removed the unnecessary method that becomes to grade after the mixture of the formation film based on sol-gal process, atomic swimming electro-deposition, the porous based on blowing agent, coating and polymer particles etc. is arranged, but is not limited in this.

Dielectric substrate 615 soaks electrolyte to be contained in the oxide semiconductor porous layer 613 and forms, or after electrolyte being soaked be contained in the oxide semiconductor porous layer 613, use suitable gelating agent and make electrolyte gelation (imitative cure) and integrally formed with oxide semiconductor porous layer 613.

As the 2nd substrate 616, can use and the 1st substrate 611 identical materials, or can use metallic plate, synthetic resin board etc. owing to do not need to have light transmission especially.

Conducting film 617 is in order to give the 2nd substrate 616 conductivity, and the film that is constituted by metals such as paper tinsel, carbon etc. that on one face 616a, forms.Conducting film 617 can use the heat treatment behind for example evaporation, sputter, the coating chlorination platinic acid and the layer of the carbon that forms or platinum etc. as long as possess electrode function, is not particularly limited.

Can use foamed polyethylene, foamed polyurethane, cellular rubber etc. as elastomeric element 619.

In dye-sensitized solar cell 610, by utilizing basket 630 sealing duplexers 620, and apply external force in the direction of the Surface Vertical of duplexer 620 upper edges and this duplexer.By making elastomeric element 619 between between to the utmost point 618 and body 631, and can be by this external force inhibitory action utmost point 614 and between the utmost point 618 lateral shift taking place.And, by elastomeric element 619, can make duplexer 620 keep being firmly fixed at basket 630 in the flexibility in direction with the Surface Vertical of this duplexer.

The material that forms body 631 is not particularly limited, and can use various metals, pottery, various synthetic resin etc.

Lid 632 can use the parts that have through the optical characteristics of sunlight.Parts with the optical characteristics that sees through sunlight are not particularly limited, and for example can enumerate parts transparent by propylene, Merlon, polyvinyl chloride, soda-lime glass etc. and that the material tool rigidity constitutes.

Seal member 641 can use by acrylonitrile-butadiene rubber, silicon rubber, polyurethane rubber, contain O type circle that fluorubber elastomeric material or polytetrafluoroethylene etc. constitute, pad etc.

As screw 642,, can use so long as lid 632 can be engaged, is fixed in body 631.

And, in this example, as the parts that lid 632 engaged, are fixed in body 631 and illustration screw 642, but the photo-electric conversion element of the 5th execution mode of the present invention is not limited to this.In the photo-electric conversion element of the 5th execution mode of the present invention, as the parts that lid engaged, are fixed in framework, can use the tabular fastener card of hinge that for example will rotatably be located on the lid to end the parts that sandwich the tightening power of spring of the sleeve-like that is the コ font by the parts of fastener, the section that utilizes mode according to frame portion, press section and the top surface of contact framework to be installed in the basket outside of being located at framework.And, aforementioned fastener is limited to also to be can be by the parts of fastener fitting portion is embedded in by the parts of fitting portion.

As described above, in dye-sensitized solar cell 610, behind the assembling duplexer 620, do not need electrolyte is filled in the effect utmost point 614 and between the utmost point 618, so can simplify working process.And the sealing material that dye-sensitized solar cell 610 need be made of thermoplastic resin etc. is so that weatherability is a long-term reliability is good.And, the effect utmost point 614 of dye-sensitized solar cell 610 and to not needing to be provided with distance between the utmost point 618, so excellent in power generation efficiency.

And, in dye-sensitized solar cell 610, lid 632 removably is fixed in body 631 by seal member 641, and duplexer 620 utilizes basket 630 sealings, so duplexer 620 takes place can it be pulled down and repair or be replaced with qualified product from basket 630 under the bad situation.And, because reusable basket 630, so can cut down manufacturing cost.

Secondly, one example of manufacture method of the photo-electric conversion element of the 5th execution mode of the present invention is described with reference to Figure 13.

In this example, at first prepare to go up and the effect utmost point 614 that constitutes with the face 611a that preordering method sequentially is formed on nesa coating 612 and oxide semiconductor porous layer 613 the 1st substrate 611.

Then, the electrolyte that has added gelating agent in advance dripped and soak be contained in oxide semiconductor porous layer 613 after, make this electrolyte gelation, form the dielectric substrate 615 that constitutes one with oxide semiconductor porous layer 613.

Then, according to the mode that the bottom surface 631a that makes by elastomeric element 619 inboard of another face 618b of the utmost point 618 and body 631 joins, the configuration effect utmost point 614 in body 631.

Then, according to making conducting film 617 be overlapped in the mode of dielectric substrate 615, will overlap on the effect utmost point 613 utmost point 618, and will be formed in the body 631 with the duplexer 620 that the effect utmost point 614 forms with the utmost point 618 is clipped dielectric substrate 615.

Then, the mode according to another face 614b of the covering effect utmost point 614 disposes lid 632.

Then, on one side from the outside of lid 632 towards with the direction imposed load of the duplexer Surface Vertical of duplexer 620, one side is by seal member 641 and utilize screw 642 that lid 632 is fixed in body 631, with basket 630 sealing duplexers 620, thereby obtain dye-sensitized solar cell 610.

Among Figure 14, label 650 be expressed as dye-sensitized solar cell, 651 be the 1st substrate, 652 for nesa coating, 653 for the oxide semiconductor porous layer, 654 for the effect utmost point, 655 for dielectric substrate, 656 be the 2nd substrate, 657 for conducting film, 658 for to the utmost point, 659 for elastomeric element, 660 for duplexer, 670 for basket (being also referred to as " body " sometimes), 681 for seal member, 682 for screw.

This dye-sensitized solar cell 650 is roughly by constituting with the lower part: face 654a be provided with the effect utmost point 654 that makes sensitizing coloring matter be supported at the oxide semiconductor porous layer 653 on surface, with a face 654a subtend dispose to the utmost point 658, be formed at a face 654a and to the subtend of the utmost point 658 between face (to call " face " in the following text) 658a of this face dielectric substrate 655 and the basket 670 of taking in above-mentioned parts.

And in this dye-sensitized solar cell 650, dielectric substrate 655 is integrally formed with oxide semiconductor porous layer 653.

The effect utmost point 654 has the 1st substrate 651 and order forms on one face 651a nesa coating 652 and oxide semiconductor porous layer 653.And, at the circumference 654c of the effect utmost point 654 oxide semiconductor porous layer 653 is not set, but constitutes with nesa coating 652 by the 1st substrate 651.

The utmost point 658 is had the 2nd substrate 656 and is formed at conducting film 657 on the one face 656a.

In dye-sensitized solar cell 650, to act on the utmost point 654 and the utmost point 658 is clipped dielectric substrate 655 formed duplexers 660 as photo-electric conversion element performance function.

In dye-sensitized solar cell 650, duplexer 660 is accommodated in the body 670 of section concavity, and the side 660a that this body 670 coats duplexer 660 reaches another face 658b to the utmost point 658.And body 670 is by elastomeric element 659 and join with another face 658b to the utmost point 658.

And the circumference 654c of the effect utmost point 654 directly contacts with body 670 by seal member 681.And the circumference 654c of the effect utmost point 654 utilizes screw 682 to be fixed in body 670.

And, in order fully to guarantee the sealing of 670 pairs of duplexers 660 of body, the face 654d that joins with body 670 of face 670a that joins with circumference 654c that is preferably in body 670 and circumference 654c goes up the fitting portion (omitting diagram) that has in order to the ditch of chimeric seal member 681 etc. is set.

By forming this structure, covered by basket 670 and under the state of pushing with this duplexer Surface Vertical direction, duplexer 660 is sealed by basket 670 Integrativelies at the side of duplexer 660 660a region-wide.

The 1st substrate 651 uses and above-mentioned the 1st substrate 611 identical materials.

It is identical with above-mentioned nesa coating 612 that nesa coating 652 is set to.

The semiconductor that forms oxide semiconductor porous layer 653 can use and form the semiconductor identical materials of above-mentioned oxide semiconductor porous layer 613.

Sensitizing coloring matter can use and the above-mentioned the 1st routine identical materials.

It is identical with above-mentioned dielectric substrate 615 that dielectric substrate 655 is set to.

Electrolyte uses and the identical electrolyte of above-mentioned the 1st example.

Gelating agent uses and the identical gelating agent of above-mentioned the 1st example.

The 2nd substrate 656 uses and above-mentioned the 2nd substrate 616 identical materials.

It is identical with above-mentioned conducting film 617 that conducting film 657 is set to.

Elastomeric element 659 uses and above-mentioned elastomeric element 619 identical materials.

The material that forms basket 670 is not particularly limited, and can use and form the material identical materials of above-mentioned body 631.

Seal member 681 uses and above-mentioned seal member 641 identical materials.

Screw 682 uses and above-mentioned screw 642 identical materials.

And, in this example, as acting on that the utmost point 654 engages, is fixed in the parts of basket 670 and illustration screw 682, but the photo-electric conversion element of the 5th execution mode of the present invention is not limited to this.In the photo-electric conversion element of the 5th execution mode of the present invention, as the parts that lid engaged, are fixed in framework, for example can use the tabular fastener card of will the effect that rotatably is located at extremely going up of hinge to end the parts that sandwich the tightening power of spring of the sleeve-like that is the コ font by the parts of fastener, the section that utilizes mode according to the contact action utmost point and basket surface to be installed in its outside of being located at basket.And, aforementioned fastener is limited to also to be can be by the parts of fastener fitting portion is embedded in by the parts of fitting portion.

As described above, in dye-sensitized solar cell 650, after assembling duplexer 660, do not need electrolyte is filled in the effect utmost point 654 and between the utmost point 658, so can simplify working process.And the sealing material that dye-sensitized solar cell 650 need not be made of thermoplastic resin etc. is so that weatherability is a long-term reliability is good.And, the effect utmost point 654 of dye-sensitized solar cell 650 and to not needing to be provided with distance between the utmost point 658, so excellent in power generation efficiency.

And, the lid of the effect utmost point 654 double as baskets 670, the part of the participation generating of the effect utmost point 654 not tegmentum covers, and therefore can suppress to inject the minimizing of light quantity of part of the participation generating of the effect utmost point 654, therefore, dye-sensitized solar cell 650 has more excellent generating efficiency.

And, in dye-sensitized solar cell 650, the effect utmost point 654 removably is fixed in basket 670 by seal member 681, the effect utmost point 654 directly joins with basket 670, and duplexer 660 is sealed by basket 670, so take place it to be pulled down and to repair or to be replaced with qualified product from basket 670 under the bad situation at duplexer 660.And, because reusable basket 670, so can cut down manufacturing cost.

The photo-electric conversion element of the 5th execution mode of the present invention, assembling do not need electrolyte is filled in the effect utmost point behind the duplexer and to the utmost point between, so can simplify working process.And the sealing material that the photo-electric conversion element of the 5th execution mode of the present invention need be made of thermoplastic resin etc. is so that weatherability is a long-term reliability is good.And the photo-electric conversion element of the 5th execution mode of the present invention need not be provided with distance at the effect utmost point and between to the utmost point, so the generating efficiency excellence.

And, the lid of the effect utmost point double as body of the photo-electric conversion element of the 5th execution mode of the present invention, the part of the participation generating of the effect utmost point not tegmentum covers, therefore can suppress to inject the minimizing of light quantity of part of the participation generating of the effect utmost point, therefore, dye-sensitized solar cell has more excellent generating efficiency.And the effect utmost point removably is fixed in the body of basket, and the effect utmost point and body directly join, and duplexer is sealed by body, so take place can it be pulled down and repair or be replaced with qualified product from body under the bad situation at duplexer.And, because reusable body, so can cut down manufacturing cost.

And, in the photo-electric conversion element of the 5th execution mode of the present invention, make elastomeric element between between to the utmost point and basket, even apply external force towards direction with the duplexer Surface Vertical, also can the inhibitory action utmost point and to lateral shift takes place between the utmost point.And, can utilize elastomeric element and make duplexer keep flexibility and be firmly fixed at basket with the direction of this duplexer Surface Vertical.

Utilizability on the industry

According to the 1st execution mode of the present invention, can provide a kind of photo-electric conversion element that has excellent long-time stability and can provide with low price.Have with the structure of the effect utmost point by adopting in basket, to take in the battery component parts that the utmost point is clipped the duplexer that dielectric substrate forms, and can reach simply and being connected of external circuit, therefore the photo-electric conversion element of the 1st execution mode of the present invention can shorten the needed time of construction significantly.

According to the 2nd execution mode of the present invention, can provide a kind of remain in the dye-sensitized semi-conducting electrode to fill and inject aqueous or gelatinous electrolytical advantage, and have the photo-electric conversion element and the manufacture method thereof of excellent generating efficiency.Therefore, the 2nd execution mode of the present invention is injected light quantity and is realized high output characteristic increasing by the shared effect utmost point and lid, and the manufacturing of photo-electric conversion element that has the long-time stability of output characteristic concurrently contributes.

According to the 3rd execution mode of the present invention, can be applied to as dye-sensitized solar cell to sandwich the state of electrolyte or gel-like electrolyte, make the overlap action utmost point and the duplexer that the utmost point is formed be sealed in the photo-electric conversion element of the structure in the basket.

According to the 4th, 5 execution modes of the present invention, can realize keeping easily to fill high viscosity or gelatinous electrolytical advantage, and energy efficiency is collected the dye-sensitized solar cell of the electronics of generation well.And, owing to can not reduce the light quantity of injecting battery, and also high with the separation property of basket, therefore can realize maintenance property and reclaim the solar cell that recirculation is also high, carrying capacity of environment is low.

Claims

1. photo-electric conversion element, it has:

Duplexer; And take in the basket of aforementioned duplexer,

Aforementioned duplexer has:

The effect utmost point is provided with the oxide semiconductor porous layer that sensitizing coloring matter is supported at the surface in one face;

To the utmost point, with the aforementioned effect utmost point aforementioned one in the face of to configuration;

Dielectric substrate, it is formed at the aforementioned effect utmost point and aforementioned between the utmost point; And

Electric conductor, its mode according to the side that surrounds aforementioned oxide semiconductor porous layer is provided with,

Aforementioned basket has:

Framework, it covers aforementioned duplexer; And

Lid, it is fixed in aforementioned framework with aforementioned duplexer,

Wherein, aforementioned framework covers in aforementioned effect extremely and the corresponding zone, position that is formed with aforementioned electric conductor.

2. photo-electric conversion element as claimed in claim 1, wherein aforementioned electric conductor is arranged on the circumference of the aforementioned effect utmost point.

3. photo-electric conversion element as claimed in claim 1, wherein aforementioned lid removably is fixed in aforementioned framework.

4. photo-electric conversion element as claimed in claim 1, wherein also have be located at aforementioned to the elastomeric element between the utmost point and the aforementioned lid.