CN1819276A - Sensitive dye solar battery with nanometer crystal TiO2 - Google Patents

Sensitive dye solar battery with nanometer crystal TiO2 Download PDF

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Publication number
CN1819276A
CN1819276A CN 200610011138 CN200610011138A CN1819276A CN 1819276 A CN1819276 A CN 1819276A CN 200610011138 CN200610011138 CN 200610011138 CN 200610011138 A CN200610011138 A CN 200610011138A CN 1819276 A CN1819276 A CN 1819276A
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electrode
solar cell
tio
storage tank
fluid infusion
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CN100555673C (en
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万发荣
胡宇宁
姜春华
龙毅
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

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Abstract

The invention consists of semiconductor electrode, liquid electrolyte, counter electrode and sealing materials. It mounts an aqua storage tank in use for storing liquid electrolyte and liquid supplementary channel for use in supplying liquid electrode from outside of TiO2 solar cell. More electrolytes stored in inside of TiO2 solar cell can keep a long working life, and supplementary of electrolyte from outside can avoid failure of TiO2 solar cell caused by leakage or volatile of electrolyte.

Description

Dye sensitized nano crystal body TiO 2Solar cell
Technical field
The invention belongs to technical field of solar batteries, a kind of dye sensitized nano crystal body TiO particularly is provided 2Solar cell especially relates to and a kind ofly possesses the electrolytical liquid storage tank of storing liquid and from this dye sensitized nano crystal body TiO 2The outside of solar cell replenishes the dye sensitized nano crystal body TiO of the fluid infusion passage of liquid electrolyte to liquid storage tank 2Solar cell.
Background technology
Dye sensitized nano crystal body TiO 2Solar cell is (hereinafter to be referred as TiO 2Solar cell) with its good performance with low-cost obtain people's attention, and obtained developing rapidly in surplus ten year, be considered to one of the most promising developing direction of following photovoltaic generation.At present, the research work in this field relates to various aspects such as semiconductor film material, dyestuff, electrolyte, electro-conductive glass, encapsulation technology.
The TiO in past 2The structure of solar cell as shown in Figure 1.As this TiO 2An electrode of solar cell, promptly so-called semi-conducting electrode 1 has nanocrystal TiO in the surface-coated of the electro-conductive glass of being made up of glass substrate 10 and conductive film 11 2 Film 2, nanocrystal TiO 2Be adsorbed with sensitizing dyestuff 3 on the film 2.As TiO 2Another electrode of solar cell, promptly so-called to electrode 6, in the surface-coated of the electro-conductive glass of forming by glass substrate 60 and conductive film 61 catalyst such as platinum or carbon are arranged.Semi-conducting electrode 1 and electrode 6 combined by encapsulant 7.At semi-conducting electrode 1 with between, be filled with liquid electrolyte 5 to electrode 6.TiO 2Solar cell absorbs the energy of sunlight effectively by sensitizing dyestuff 3, and will electrons excited be injected into nanocrystal TiO in sensitizing dyestuff 3 when work 2In the conduction band of film 2.And be injected into nanocrystal TiO 2Electronics in the conduction band of film 2 is sent to again and nanocrystal TiO 2On the conductive film 11 that film 2 combines, arrive electrode 6 through overload 4 then.The effect of liquid electrolyte 5 then is with to being transmitted electronically on the sensitizing dyestuff 3 on the electrode 6.Platinum on the electrode 6 or carbon as catalyst, are promoted the electron transfer on the electrode 6 to liquid electrolyte 5.
TiO 2The subject matter that solar cell faces now is the battery shortening in useful life, is because TiO and cause a main cause of battery shortening in useful life 2Adopt liquid electrolyte in the solar cell, and liquid electrolyte As time goes on, might let out because of volatilization from battery, thereby cause TiO 2The inefficacy of solar cell.
As solving the method that above-mentioned liquid electrolyte volatilization is leaked, can improve the cell package technology and adopt solid electrolyte.
TiO 2Solar cell generally adopts organic encapsulants such as epoxy resin that battery is sealed.But the easy ageing failure of organic encapsulant, thereby the volatilization that has aggravated liquid electrolyte is leaked.Can adopt the better low-melting glass of sealing effectiveness as the technology of encapsulant (Cai Chunping, the research of low melting point crystallite seal glass, Application Optics, 1995,16, pp.33-39).But other elements that contain in the low-melting glass (for example lead etc.) might interact with the iodine in the liquid electrolyte, and then influence electrolytical effect.
In addition, adopt solid electrolyte to replace liquid iodine electrolyte, can avoid electrolyte volatilization problem (Li Bin, Qiu Yong, DSSC, photographic science and chemistry, 2000,18 (4), pp.336-347).But the ion migration rate of solid electrolyte is lower than the ion migration rate of liquid electrolyte, thereby makes the TiO of solid electrolyte 2The photoelectric conversion efficiency of solar cell is lower than the TiO of liquid electrolyte 2The photoelectric conversion efficiency of solar cell.
Summary of the invention
The objective of the invention is to: a kind of dye sensitized nano crystal body TiO is provided 2Solar cell, a kind of possess the electrolytical liquid storage tank of storing liquid and from this TiO 2The outside of solar cell replenishes the TiO of the fluid infusion passage of liquid electrolyte to liquid storage tank 2Solar cell, thus can overcome the problem that the volatilization of liquid electrolyte is leaked, avoid the low of the photoelectric conversion efficiency that causes because of solid electrolyte simultaneously again.
The present invention includes: semi-conducting electrode 1, liquid electrolyte 5, electrode 6, encapsulant 7.The present invention be provided be used for the electrolytical liquid storage tank 51 of storing liquid, from dye sensitized nano crystal body TiO 2The outside of solar cell replenishes the fluid infusion passage 52 of liquid electrolyte to liquid storage tank 51, liquid storage tank 51 is arranged on the one side towards semi-conducting electrode 1 to electrode 6, because liquid storage tank 51 is arranged on the one side towards semi-conducting electrode 1 to electrode 6, thereby carries out TiO easily 2The assembling of solar cell.
Because TiO 2There is liquid storage tank 51 in inside solar energy battery, has increased TiO 2The quantity of the liquid electrolyte of inside solar energy battery, thus TiO prolonged 2The useful life of solar cell.And, because be provided with fluid infusion passage 52, work as TiO 2The liquid electrolyte 5 of inside solar energy battery can be opened the encapsulant 7 at fluid infusion passage 52 places after leaking owing to volatilizing and reducing, and replenishes liquid electrolytes 5 by fluid infusion passage 52, and then has prolonged TiO more 2The useful life of solar cell.
On one side to the above-mentioned dorsad semi-conducting electrode 1 of electrode 6, be coated with cover plate 64, liquid storage tank 51 is arranged on the one side to the backside semiconductor electrode 1 of electrode 6, and the liquid electrolyte 5 in the liquid storage tank 51 can be by being arranged on the above-mentioned one side towards above-mentioned semi-conducting electrode 1 that through hole on the electrode 1 63 is arrived electrode 6.Liquid storage tank 51 is arranged on the one side to the backside semiconductor electrode 1 of electrode 6, thereby the liquid storage tank 51 of big volume can be set, and can not influence the catalytic effect to electrode 6 owing to the setting of liquid storage tank 51.
On one side to the backside semiconductor electrode 1 of electrode 6, be coated with cover plate 64, liquid storage tank 51 be arranged on cover plate 64 towards one side to electrode 6, the above-mentioned liquid electrolytes 5 in the liquid storage tank 51 can above-mentionedly arrive the above-mentioned one side towards above-mentioned semi-conducting electrode 1 to electrode 6 to the through hole on the electrode 6 63 by being arranged on.Since liquid storage tank 51 be arranged on cover plate 64 towards surface to electrode 6, on to electrode 6, only be provided with through hole 63, thereby the liquid storage tank 51 of volume greatly can be set, and can not influence catalytic effect owing to the setting of liquid storage tank 51, simplify manufacture craft simultaneously electrode 6 to electrode 6.
Fluid infusion passage 52 be arranged on to electrode 6 on the one side of semi-conducting electrode 1, surperficial parallel with to electrode 6.Because fluid infusion passage 52 surperficial parallel with to electrode 6, so can reduce dye sensitized nano crystal body TiO 2The integral thickness of solar cell makes things convenient for TiO 2Installing and using of solar cell.
Fluid infusion passage 52 is arranged on the electrode 6, with above-mentioned Surface Vertical to electrode 6.Because fluid infusion passage 52 and Surface Vertical to electrode 6 therefore can be at TiO 2 Fluid infusion passage 52 is set near the center of solar cell, thereby accelerates to replenish the operation of liquid electrolyte.
Fluid infusion passage 52 be arranged on cover plate 64 towards one side to electrode 6, surperficial parallel with cover plate 64.Because fluid infusion passage 52 is surperficial parallel with cover plate 64, therefore can reduce dye sensitized nano crystal body TiO 2The integral thickness of solar cell makes things convenient for TiO 2Installing and using of solar cell.
Fluid infusion passage 52 is arranged on the cover plate 64, with the Surface Vertical of cover plate 64.Because the Surface Vertical of fluid infusion passage 52 and cover plate 64 therefore can be at TiO 2 Fluid infusion passage 52 is set near the center of solar cell, thereby accelerates to replenish the process of liquid electrolyte.
Liquid passage 52 of the present invention has 2～10.Therefore when replenishing liquid electrolyte, wherein at least 1 fluid infusion passage is as the exhaust passage, thereby accelerates the process of additional liquid electrolyte.
The invention effect:
TiO of the present invention 2Solar cell is owing to having liquid storage tank and fluid infusion passage, at TiO 2Inside solar energy battery can store more liquid electrolyte, can make TiO 2Solar cell is kept long working life, simultaneously when liquid electrolyte reduces because of the volatilization leakage, can open the encapsulant at fluid infusion passage place, replenish liquid electrolyte, thereby can avoid causing TiO because of the volatilization leakage of liquid electrolyte by the fluid infusion passage 2The inefficacy of solar cell.
Description of drawings
Fig. 1 is TiO in the past 2The structural representation of solar cell.Wherein, semi-conducting electrode 1, glass substrate 10, conductive film 11, nanocrystal TiO 2Film 2, load 4, liquid electrolyte 5, to electrode 6, encapsulant 7, glass substrate 60, conductive film 61, Pt film 62.
Fig. 2 is the front view to electrode of the embodiment of the invention 1.Wherein, liquid storage tank 51, fluid infusion passage 52.
Fig. 3 is the vertical view to electrode of the embodiment of the invention 1.
Fig. 4 is the TiO of the embodiment of the invention 1 2The structural representation of solar cell.
Fig. 5 represents the TiO of the embodiment of the invention 1 2The short circuit current of solar cell over time.
Fig. 6 represents the TiO of the embodiment of the invention 1 2The open circuit voltage of solar cell over time.
Fig. 7 is the front view to electrode of the embodiment of the invention 2.Wherein, through hole 63.
Fig. 8 is the vertical view to electrode of the embodiment of the invention 2.
Fig. 9 is the TiO of the embodiment of the invention 2 2The structural representation of solar cell.Wherein, cover plate 64
Figure 10 represents the TiO of the embodiment of the invention 2 2The short circuit current of solar cell over time.
Figure 11 is the front view to electrode of the embodiment of the invention 3.
Figure 12 is the vertical view to electrode of the embodiment of the invention 3.
Figure 13 is the front view of the cover plate of the embodiment of the invention 3.
Figure 14 is the vertical view of the cover plate of the embodiment of the invention 3.
Figure 15 is the TiO of the embodiment of the invention 3 2The structural representation of solar cell.
Figure 16 represents the TiO of the embodiment of the invention 3 2The short circuit current performance of solar cell over time.
Figure 17 is the front view of the cover plate of the embodiment of the invention 4.
Figure 18 is the vertical view of the cover plate of the embodiment of the invention 4.
Figure 19 is the TiO of the embodiment of the invention 4 2The structural representation of solar cell.
Figure 20 represents the TiO of the embodiment of the invention 4 2The short circuit current of solar cell over time.
1 semi-conducting electrode, 10 glass substrates, 11 conductive films, 2 nanocrystal TiO 2Film, 4 loads, 5 liquid electrolytes, 51 liquid storage tanks, 52 fluid infusion passages, 6 pairs of electrodes, 60 glass substrates, 61 conductive films, 62Pt film, 63 through holes, 64 cover plates, 7 encapsulants
Embodiment
With reference to the accompanying drawings, the embodiments of the invention attitude is described.
Embodiment 1
Basis material used during preparation semi-conducting electrode 1 is cut into 2.5cm * 2.5cm size for face resistance is the ITO electro-conductive glass of 20-30 ohm, cleans up then.Employed nanocrystal TiO 2Powder is industrial P25 type TiO 2Powder, its average grain diameter are 25-30nm, and specific area is 50m 2/ g, TiO 2Content is anatase and rutile mixed structure mutually greater than 99.5%.Adopt the powder coating method on the ITO electro-conductive glass, to prepare TiO 2Film, its process is: 8mL deionized water and 1.0g P25 powder are fully mixed the back add the slurry that is mixed with suspension-turbid liquid after several PEG also fully grind, prepared slurry is spread upon on the ITO electro-conductive glass of having cut out and having cleaned up equably, 450 ℃ of insulations 60 minutes.To be coated with TiO then 2The ITO electro-conductive glass of film is put into dye solution and is soaked.Used dyestuff is the N3 dyestuff, adopts absolute ethyl alcohol to be mixed with dye solution as solvent, and dye strength is 0.3g/L.Dyestuff soak the back to semi-conducting electrode 1 clean, drying.
Preparation during to electrode 6 used basis material be cut into 2.5cm * 2.5cm size for face resistance is 20-30 ohm ITO electro-conductive glass.To electrode 6 towards the one side of semi-conducting electrode 1, promptly have the one side of conductive film 11, utilize the hydrofluoric acid corrosion, form the liquid storage tank 51 and the fluid infusion passage 52 of shape shown in Fig. 2,3.Utilize chemical plating method then, preparation Pt film on the ITO electro-conductive glass.The employed electroplate liquid of chemical plating is: 0.5gH 2PtCl 4.6H 2O, 5g (NH 4) 2HPO 4, 15gNa 2HPO 4Be mixed with the aqueous solution of 100ml, heating for dissolving becomes orange transparent aqueous solution, adds a certain amount of NaOH then and reconciles pH value to 8.Electroplate liquid will maintain 80 ℃ during plating, and voltage is 4-5V.
Liquid electrolyte is lithium iodide (LiI) and iodine (I 2) carbonic allyl ester solution, wherein the concentration of lithium iodide (LiI) is 0.5M, iodine (I 2) concentration be 0.05M, solvent is a propene carbonate.
Utilize epoxy sealing TiO 2Solar cell.Resulting TiO 2The structure of solar cell as shown in Figure 4.When liquid electrolyte reduces because of the volatilization leakage, remove the encapsulant 7 at fluid infusion passage 52 places, replenish liquid electrolytes 5 by fluid infusion passage 52, and then utilize epoxy resin that fluid infusion passage 52 is sealed.
The TiO of Fig. 5,6 expression embodiment 1 2The time dependent relation of the short circuit current of solar energy and open circuit voltage.From Fig. 5,6 as can be known, along with the volatilization of liquid electrolyte 5, TiO 2The short circuit current of solar cell can reduce gradually, but open-circuit does not obviously descend.After replenishing liquid electrolyte 5 (position shown in the arrow among the figure), short circuit current gos up significantly.
Embodiment 2
The semi-conducting electrode 1 of present embodiment, liquid electrolyte 5 and encapsulating method are all identical with embodiment 1.As different from Example 1, in the present embodiment,, utilize the hydrofluoric acid corrosion, form liquid storage tank 51 and fluid infusion passage 52, on to electrode 6, form through hole 63 simultaneously, shown in Fig. 7,8 in one side to the backside semiconductor electrode 1 on the electrode 6.In addition, in the present embodiment, has cover plate 64.This cover plate 64 is an one flat plate glass, is used to cover to liquid storage tank on the electrode 6 51 and fluid infusion passage 52.Here omit illustrating of cover plate 64.Resulting TiO 2The structure of solar cell as shown in Figure 9.
Figure 10 represents the TiO of embodiment 2 2The time dependent relation of the short circuit current of solar cell.As can be seen from Figure 10, along with the volatilization of liquid electrolyte, TiO 2The short circuit current of solar cell can reduce gradually.But because the volume of liquid storage tank 51 is greater than embodiment 1, thus short circuit current to reduce required time longer than embodiment 1.After replenishing liquid electrolyte 5, short circuit current gos up significantly.The TiO of embodiment 2 2The variation of the open circuit voltage of solar cell is identical with embodiment 1, omits explanation here.
Embodiment 3
The semi-conducting electrode 1 of present embodiment, liquid electrolyte 5 and encapsulating method are all identical with embodiment 2.
As different from Example 2, in the present embodiment, on to electrode 6, offer through hole 63, shown in Figure 11,12.The one side towards to electrode 6 of cover plate 64 is provided with liquid storage tank 51 and fluid infusion passage 52, shown in Figure 13,14.Resulting TiO 2The structure of solar cell as shown in figure 15.
Figure 16 represents the TiO of embodiment 3 2The time dependent relation of the short circuit current of solar cell.As can be seen from Figure 16, the TiO of embodiment 3 2The function of solar cell and embodiment 2 are roughly the same.The TiO of embodiment 3 2The variation of the open circuit voltage of solar cell is identical with embodiment 2, omits explanation here.
Because liquid storage tank 51 and fluid infusion passage 52 among the embodiment 3 all are arranged on the cover plate 64,, therefore simplified preparation technology to electrode 6 to only being provided with through hole 63 on the electrode 6.
Embodiment 4
The semi-conducting electrode 1 of present embodiment, liquid electrolyte 5, liquid storage tank 51 and encapsulating method are all identical with embodiment 3.
As different from Example 3, in the present embodiment, fluid infusion passage 52 is arranged near the planar central of cover plate 64, shown in Figure 17,18.Resulting TiO 2The structure of solar cell as shown in figure 19.
Figure 20 represents the TiO of embodiment 4 2The time dependent relation of Solar cell performance.As can be seen from Figure 20, the TiO of embodiment 4 2The function of solar cell and embodiment 3 are roughly the same.
Because liquid storage tank 51 and fluid infusion passage 52 among the embodiment 4 all are arranged on the cover plate 64,, therefore simplified preparation technology to electrode 6 to only being provided with through hole 63 on the electrode 6.In addition, because fluid infusion passage 52 is arranged near the planar central of cover plate 64, near liquid storage tank 51, therefore the liquid electrolyte 5 that replenishes can arrive liquid storage tank 51 quickly, thereby has shortened the required time of additional liquid electrolyte 5.
The foregoing description 1-4 only is explanation content of the present invention, but the present invention is not limited thereto.For example, in embodiment 1-4, liquid storage tank be shaped as rectangle, obvious liquid storage tank of the present invention also can be for different shapes such as circle, ellipses, as long as have the electrolytical function of storing liquid.In embodiment 1-4, utilize the hydrofluoric acid corrosion to form liquid storage tank and fluid infusion passage, also can form liquid storage tank and fluid infusion passage by additive methods such as mechanical polishinges.In addition, in embodiment 1-4, adopted 1 cover plate, to constitute liquid storage tank and fluid infusion passage.But also can adopt the cover plate more than 2 or 2, to constitute bigger liquid storage tank of volume and more fluid infusion passage.

Claims (8)

1, a kind of dye sensitized nano crystal body TiO 2Solar cell comprises semi-conducting electrode, liquid electrolyte, to electrode, encapsulant, it is characterized in that: be provided be used for the electrolytical liquid storage tank of storing liquid (51), from dye sensitized nano crystal body TiO 2The outside of solar cell is to the fluid infusion passage (52) of the additional liquid electrolyte of liquid storage tank (51), and liquid storage tank (51) is arranged on the one side towards semi-conducting electrode (1) to electrode (6).
2, dye sensitized nano crystal body TiO according to claim 1 2Solar cell, it is characterized in that: on one side the above-mentioned dorsad semi-conducting electrode (1) of electrode (6), be coated with cover plate (64), liquid storage tank (51) is arranged on the one side to the above-mentioned dorsad semi-conducting electrode (1) of electrode (6), and the liquid electrolyte in the liquid storage tank (51) is above-mentioned to the one side towards semi-conducting electrode (1) of the arrival of the through hole (63) on the electrode (1) to electrode (6) by being arranged on.
3, dye sensitized nano crystal body TiO according to claim 1 2Solar cell, it is characterized in that: on one side the backside semiconductor electrode (1) of electrode (6), be coated with cover plate (64), liquid storage tank (51) be arranged on cover plate (64) towards one side to electrode (6), the liquid electrolyte in the liquid storage tank (51) arrives the above-mentioned one side towards above-mentioned semi-conducting electrode (1) to electrode (6) by being arranged on to the through hole (63) on the electrode (6).
4, according to each described dye sensitized nano crystal body TiO among the claim 1-3 2Solar cell is characterized in that: fluid infusion passage (52) be arranged on to electrode (6) on the one side of semi-conducting electrode (1), surperficial parallel with to electrode (6).
5, dye sensitized nano crystal body TiO according to claim 1 2Solar cell is characterized in that: fluid infusion passage (52) is arranged on on the electrode (6), with the Surface Vertical to electrode (6).
6, according to claim 2 or 3 described dye sensitized nano crystal body TiO 2Solar cell is characterized in that: fluid infusion passage (52) be arranged on cover plate (64) towards one side to electrode (6), surperficial parallel with cover plate (64).
7, according to claim 2 or 3 described dye sensitized nano crystal body TiO 2Solar cell is characterized in that: fluid infusion passage (52) is arranged on the cover plate (64), with the Surface Vertical of cover plate (64).
8, according to each described dye sensitized nano crystal body TiO among the claim 1-7 2Solar cell is characterized in that: the fluid infusion passage has 2～10, and when replenishing liquid electrolyte, wherein at least 1 fluid infusion passage is as the exhaust passage, to accelerate to replenish the process of liquid electrolyte.
CN 200610011138 2006-01-09 2006-01-09 Dye sensitized nano crystal body TiO 2Solar cell Expired - Fee Related CN100555673C (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101354969B (en) * 2008-09-16 2011-04-13 彩虹集团公司 Encapsulation technology for large area dye sensitization solar battery
WO2012013135A1 (en) * 2010-07-30 2012-02-02 北京大学 Dye sensitized solar cell
CN102903535A (en) * 2012-09-28 2013-01-30 彩虹集团公司 Method for prolonging service life of large-size dye-sensitized solar cell assembly
CN106783190A (en) * 2016-12-30 2017-05-31 上海英凡环保科技有限公司 A kind of circular electrolyte type dye sensitization solar battery device

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101354969B (en) * 2008-09-16 2011-04-13 彩虹集团公司 Encapsulation technology for large area dye sensitization solar battery
WO2012013135A1 (en) * 2010-07-30 2012-02-02 北京大学 Dye sensitized solar cell
CN102347147A (en) * 2010-07-30 2012-02-08 北京大学 Dye sensitization solar battery
CN102903535A (en) * 2012-09-28 2013-01-30 彩虹集团公司 Method for prolonging service life of large-size dye-sensitized solar cell assembly
CN106783190A (en) * 2016-12-30 2017-05-31 上海英凡环保科技有限公司 A kind of circular electrolyte type dye sensitization solar battery device
CN106783190B (en) * 2016-12-30 2018-06-19 上海英凡环保科技有限公司 A kind of circular electrolyte type dye sensitization solar battery device

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