CN102324308B - Method for improving interface caking property of dye sensitized solar cell substrate - Google Patents

Method for improving interface caking property of dye sensitized solar cell substrate Download PDF

Info

Publication number
CN102324308B
CN102324308B CN 201110179968 CN201110179968A CN102324308B CN 102324308 B CN102324308 B CN 102324308B CN 201110179968 CN201110179968 CN 201110179968 CN 201110179968 A CN201110179968 A CN 201110179968A CN 102324308 B CN102324308 B CN 102324308B
Authority
CN
China
Prior art keywords
zno
precursor polymer
dssc
fiber film
nano
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN 201110179968
Other languages
Chinese (zh)
Other versions
CN102324308A (en
Inventor
云斯宁
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xian University of Architecture and Technology
Original Assignee
Xian University of Architecture and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xian University of Architecture and Technology filed Critical Xian University of Architecture and Technology
Priority to CN 201110179968 priority Critical patent/CN102324308B/en
Publication of CN102324308A publication Critical patent/CN102324308A/en
Application granted granted Critical
Publication of CN102324308B publication Critical patent/CN102324308B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • Y02E10/542—Dye sensitized solar cells
    • 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
    • Y02E10/549—Organic PV cells

Landscapes

  • Hybrid Cells (AREA)

Abstract

The invention discloses a method for improving the interface caking property of a dye sensitized solar cell substrate. The method comprises the following steps of: 1, cleaning FTO (Fluorine or antimony doped Tin Oxide) conductive glass; annealing the FTO conductive glass; 3, preparing ZnO precursor polymer gel; 4, conducting a ZnO nano fiber film stress buffer layer; 5, autoclaving and annealing the ZnO nano fiber film stress buffer layer; 6, preparing a ZnO nano fiber film photoelectrode; and 7, constructing a nano fiber film dye sensitized solar cell (DSSC). The stress buffer layer constructed in the method can effectively release thermal stress generated between a nano fiber film working electrode and a conductive substrate, prevents the sintered ZnO nano fiber film working electrode from cracking and being broken and the working electrode from being stripped from the substrate, effectively improves the caking property of the ZnO nano fiber film working electrode and the conductive substrate, further improves the stability of the working electrode, increases photoelectric energy conversion efficiency of the DSSC, prolonging the service life of the DSSC, and has important application and popularization values.

Description

A kind of close-burning method of DSSC substrate interface of improving
Technical field
The invention belongs to solar cell and utilize technical field, be specifically related to a kind of effective ways that improve dye sensitization ZnO nano-fiber film solar cell photoelectric pole and electrically-conductive backing plate interface adhesion.
Background technology
A kind of mode that solar cell utilizes as solar energy since the nineties, has obtained development fast.Got into for 20th century, along with the fast development of photovoltaic technology, solar utilization technique is fundamentally changing production, supply and the consumption pattern of the energy.But the traditional silicon solar cell receives restriction and the raw material influence in short supply of conversion efficiency, and development is restricted, though and film and concentrating solar battery have got into the commercialization volume production, have only minority manufacturer to produce.In addition, the growth of and apparatus for production line investment amount on the low side because of conversion efficiency still can't produce significantly decline at present on cost.In view of this, the research institution of countries in the world all is placed on target on the third generation solar cell.
As third generation solar cell; Dye sensitized nano crystal salar battery (the dye sensitized solar cell of O ' Regan in 1991 and M.
Figure BDA0000072368810000011
invention particularly; DSSC); Except simple structure, on cost, also have the advantage that quite lets the people have an optimistic view of.According to the estimation of Switzerland manufacturer, 10MW, conversion efficiency are 7%, area is 50cm producing per year 2Preceding topic under, the module cost of DSSC is 1.5-1.8$/W, and present traditional silicon wafer solar cell, the module cost is 3-5$/W.By contrast, both module costs have 2-3 gap doubly.In addition, with traditional first, second in generation heliotechnics compare, DSSC provides very big flexibility at aspects such as lightweight, multicolour, pliability, the transparencys for the designer, can be integrated on the Different products, is more suitable for the use in the open air.This has further started new commercial opportunity for DSSC.Under the condition that quality, conversion efficiency and encapsulation technology are improved, the occupation rate of market of DSSC will further improve, and will become a ring indispensable in the following solar power generation at good DSSC.
Present DSSC is large with liquid electrolyte mainly, mainly by optoelectronic pole (anode), electrode (platinumization), dye well electrolyte are constituted.The photovoltaic energy conversion efficient of DSSC depends on the light capture rate of dye molecule, electron injection efficiency, the efficiency of transmission of electronics in semiconductive thin film and the electron capture efficient of FTO substrate of conductor oxidate conduction band.Desirable solar cell should have a very high efficient in photon energy range.But electronics owing to relate to different interfaces, makes this process become complicated in transmission course.The electronics that is injected in the conductor oxidate conduction band transmits in semiconductor through disperse, the electronics in the transmission can with the dye molecule of oxidation state and the I in the electrolyte 3 -Ion carries out compound and consumes, and causes the reduction of electric transmission efficient.In addition, nanometer semiconductor oxidation and FTO conductive base caking property are relatively poor, cause in the electrolyte iodide ion through the infiltration and disperse, be delivered in the conductive base, so with electronics carry out compound, thereby reduced electron capture efficient.Therefore,, must take the suitable technique means to improve caking property pitiful between nano-oxide work electrode and the FTO electrically-conductive backing plate, and then inhibition or obstruction DSSC device interfaces electronics is compound in order to obtain higher photoelectric energy transformation efficiency.
The optoelectronic pole of DSSC is by being deposited on the suprabasil conductor oxidate of electro-conductive glass FTO (like ZnO, TiO 2, SnO 2) constitute behind the nano-crystal film absorbing dye.In order to obtain desirable optoelectronic pole structure, the conductor oxidate nano structure membrane must possess: the specific area that (1) is high, to increase the adsorbance of dye molecule, improve the light capture ability; (2) good connectivity between the particle of composition nano thin-film is to guarantee the good transmission performance of electronics; (3) the good caking property of nano thin-film optoelectronic pole and electrically-conductive backing plate to guarantee the good electron collection efficient of electrically-conductive backing plate, reduces the compound of interface electronics; (4) film inside has suitable space and passage, to guarantee dyestuff and electrolyte effective diffusion of portion within it.In the building process of semiconductor nano crystalline film photoelectric electrode, sintering is an indispensable technical process.Because the thermal coefficient of expansion of semiconductor nano film and electrically-conductive backing plate is different, the elongation strain that sintering process produces often causes the contraction of nano-crystal film on the electrically-conductive backing plate, causes nano-crystal film cracking and fracture, or comes off from electrically-conductive backing plate.It is all poor that these defectives cause forming the interface adhesion of connectivity, nano thin-film optoelectronic pole and electrically-conductive backing plate between the particle of nano thin-film; Electrically-conductive backing plate is directly contacted with electrolyte easily; Increase the chance of electron recombination, reduced the transmission performance and the collection efficiency of electronics.In addition, these defectives also cause the decline of unit are semiconductor-on-insulator nano-crystal film distributed mass, have reduced the adsorbance of dye molecule.Therefore; Guaranteeing that nano-crystalline photoelectric has under the condition of enough porositys; How to reduce or suppress nano-crystal film optoelectronic pole surface cracking and fracture, improve nano thin-film optoelectronic pole and the good caking property of electrically-conductive backing plate, be the important channel of raising DSSC photovoltaic energy conversion efficient.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of effective ways that improve dye sensitization ZnO nano-fiber film solar cell photoelectric pole and electrically-conductive backing plate interface adhesion are provided.This method can prevent effectively that cracking, fracture and the work electrode of ZnO nano-fiber film work electrode peels off from electrically-conductive backing plate behind the sintering; Help to suppress the compound of interface electronics, increase efficiency of transmission and electronics the collection efficiency on electrically-conductive backing plate of electronics in nano-crystal film.
In order to achieve the above object; The method that the present invention adopts electric spining technology to prepare stress-buffer layer is improved dye sensitization ZnO nano-fiber film solar cell photoelectric pole and substrate interface caking property; Promptly make up stress-buffer layer at dye-sensitized nano fiber membrane solar cell conductive glass conducting surface; The thermal stress that this stress-buffer layer effectively produces between relieving light electrode and the FTO substrate interface; Stop cracking and the fracture of ZnO nano-fiber film optoelectronic pole behind the sintering and coming off from the electrically-conductive backing plate, make the nanofiber optoelectronic pole keep good shapes.
This kind improves the close-burning method of DSSC substrate interface, may further comprise the steps:
1) clean of FTO electro-conductive glass
The FTO electro-conductive glass is cleaned 3 times with isopropyl acetone, alcohol and deionized water successively repeatedly, and each scavenging period is 10min, then with the hot-air behind the filtration, purification at the hothouse inner drying;
2) annealing in process of FTO electro-conductive glass
The FTO electro-conductive glass is placed the tubular heater heat treatment of annealing, be warming up to 400 ℃-450 ℃ with 1-2 ℃/min speed, temperature retention time is 30-60mins, naturally cools to room temperature with stove;
3) preparation of ZnO precursor polymer gel
Hydrated salt, polymer, solvent and the catalyst of zinc are dropped in the beaker by a certain percentage, be heated to 60 ℃; At rotating speed is under the 240-400r/min, and magnetic agitation 6hrs obtains even, transparent ZnO precursor polymer gel;
4) structure of ZnO precursor polymer nanofiber membrane stress resilient coating
The ZnO precursor polymer gel of preparation is injected syringe; Send in the stainless steel spinning head pin hole with the flow of 40-60 μ l/min through syringe pump; The stainless steel spinning head is connected with high voltage source; External loads voltage is 10-15kV, and stainless steel spinning head pin hole and grounding electrode are collected the substrate spacing and remained on 10-15cm.Start electric spinning device, under electric field action, ZnO precursor polymer nanofiber is collected on the FTO electro-conductive glass of vertical syringe pump spinning head pin hole lower end, and forming thickness is the ZnO precursor nano-fiber film of 100-200nm;
5) ZnO precursor polymer nanofiber membrane stress resilient coating hot-pressing processing and sintering
1. ZnO precursor polymer nanofiber film hot-pressing is handled: the metal video disc that is heated to 120 ℃-150 ℃ on the flattening oven is placed hot pressing 10-15mins on the ZnO precursor polymer nanofiber film, and in the middle of metal video disc and ZnO precursor polymer nanofiber film, insert the thick ptfe sheet of 1-2mm;
2. ZnO precursor polymer nanofiber is film sintered: the ZnO precursor polymer nanofiber film after the hot-pressing processing is at 80 ℃ of vacuumize 24hrs; Place sintering furnace then; Be warming up to 400 ℃-450 ℃; Temperature retention time is 30-60mins, naturally cools to room temperature with stove, obtains ZnO precursor polymer nanofiber membrane stress resilient coating;
6) preparation of ZnO precursor polymer nanofiber film photoelectric electrode
On the FTO electro-conductive glass that applies ZnO precursor polymer nanofiber membrane stress resilient coating, adopt wet chemistry method to make up conductor oxidate ZnO film work electrode; Place sintering furnace then; Be warming up to 400 ℃ of-450 ℃ of sintering; Temperature retention time is 30-60mins, naturally cools to room temperature with stove, obtains the ZnO nano-fiber film optoelectronic pole of DSSC DSSC device;
7) structure of nano-fiber film DSSC
Make up battery according to M.
Figure BDA0000072368810000051
the invention construction method that dye sensitized nano crystal salar battery adopted.At first, adopt N3 or N719 dyestuff that the ZnO nano-fiber film optoelectronic pole of preparation is carried out sensitization; Then; The with holes of platinumization carried out encapsulation process to electrode and semiconductor work electrode; Utilize the capillary absorption principle to inject the electrolyte that contains iodide ion, finally sealed obtains DSSC (DSSC) device to being used to inject the aperture of electrolyte on the electrode.
Further aspect of the present invention is:
Said ZnO precursor polymer gel is formulated according to following materials based on weight:
Zinc hydrated salt 0.5-10 part;
Polymer 0.2-7 part;
Solvent 10-47 part;
Catalyst 0-4 part.
The hydrated salt of said zinc is hydration zinc acetate Zn (CH 3COO) 22H 2O, zinc sulphate hydrate ZnSO 47H 2O or nitric hydrate zinc Zn (NO 3) 26H 2A kind of among the O, purity is greater than 99.99%;
Said polymer is a kind of among polyvinyl acetate PVAc, PVAC polyvinylalcohol or the PVP PVP;
Said solvent is one or both in dimethyl formamide DMF, deionized water or the ethanol;
Said catalyst is an acetate.
The hydrated salt of said zinc or further add dopant, dopant is the hydrated sulfate Al of aluminium 2(SO 4) 3XH 2O, nitric hydrate salt Al (NO 3) 39H 2O or hydration halide salt AlCl 36H 2A kind of among the O, its purity is higher than 99.99%; The addition of dopant adds according to the atomic percentage conc 0-6atom% of doped with Al element in ZnO.
In the said step 6); Further ZnO nano-fiber film optoelectronic pole being carried out hydrothermal solution handles; ZnO nano-fiber film optoelectronic pole is immersed in the zinc acetate aqueous solution of 0.1-0.3M and keeps 5-15mins, and then the optoelectronic pole of sintering hydrothermal solution after handling.
Sintering is characterized as in said step 5), the step 6): the speed with 1-2 ℃/min is warming up to 350 ℃, stops 10-15mins, is rapidly heated to 400 ℃-450 ℃ insulation 30-60mins subsequently with 5 ℃/min of speed.
Wet chemistry method is a kind of of hydro thermal method, sol-gal process or electrical spinning method in the said step 6).
The preferred conductor oxidate of the present invention is ZnO, and wet chemistry method is an electrical spinning method.
The technique effect that the present invention brought is:
The first, through on electrically-conductive backing plate, making up resilient coating, the caking property of thin-film solar cell photoelectric pole and electrically-conductive backing plate can be improved effectively, and the photovoltaic energy conversion efficient of battery is improved significantly.
The second, the thermal stress that effectively produces between relieving light electrode and the FTO substrate interface of resilient coating; Further stop cracking and the fracture of optoelectronic pole nano-fiber film in the sintering process and coming off from the electrically-conductive backing plate, make the network configuration pattern of nanofiber optoelectronic pole keep good.
Three, use the present invention, the chance of inside battery interface electron recombination is lowered, and the power output of battery is enhanced, and the performance of battery is enhanced.
Four, electric spining technology provided by the invention and hot-pressing processing technology, operation is simple, and strong with optoelectronic pole preparation technology compatibility, and treatment effect is good, and it is obvious to improve performance.
Five, utilize the method and technology, can effectively protect optoelectronic pole, improve the performance (photovoltaic energy conversion efficient is increased to 0.55% from 0.04%) of battery.Stablizing of optoelectronic pole material property guaranteed the stable, reliable of battery performance, reached practical and long-life purpose.
Description of drawings
Fig. 1 is electric spining technology device sketch map (exemplary systems comprises high voltage source, have the syringe pump of stainless steel spinning head and be used to collect the grounding electrode substrate of fiber);
Fig. 2 is the FESEM pattern that adopts the ZnO precursor polymer nanofiber stress-buffer layer that electric spining technology makes up on the FTO electrically-conductive backing plate;
Fig. 3 is the stress-buffer layer nano-fiber film SEM pattern behind the sintering;
Fig. 4 adopts electric spining technology on the FTO electrically-conductive backing plate, to make up the FESEM pattern of optoelectronic pole;
Fig. 5 is the ZnO nanofiber optoelectronic pole film SEM pattern (not making up stress-buffer layer on the FTO electrically-conductive backing plate) that shrinks, ftractures;
Fig. 6 is the FESEM pattern (the FTO electrically-conductive backing plate does not make up stress-buffer layer) of fracture or the ZnO nano-fiber film optoelectronic pole that comes off;
Fig. 7 is the SEM pattern (use the present invention on electrically-conductive backing plate, to make up stress-buffer layer, optoelectronic pole nanofiber network structure and morphology is well kept) that the fiber pattern keeps good ZnO nanofiber optoelectronic pole behind the sintering;
Fig. 8 is that DSSC makes up sketch map (M.
Figure BDA0000072368810000071
invention dye sensitized nano crystal salar battery construction method);
Fig. 9 is employing and does not adopt the present invention to handle the contrast (resilient coating can effectively improve the photovoltaic energy conversion efficient of battery) of electrically-conductive backing plate DSSC battery performance.
Embodiment
In order to specify technology contents of the present invention, characteristic and effect, below in conjunction with embodiment and be equipped with accompanying drawing the present invention is further described.It is emphasized that the present invention is not limited to following embodiment.
Practical implementation step of the present invention is following:
1) clean of FTO electro-conductive glass:
The FTO electro-conductive glass is cleaned 3 times with isopropyl acetone, alcohol and deionized water successively repeatedly, and each scavenging period is 10mins, then with the hot-air behind the filtration, purification at the hothouse inner drying.
2) annealing in process of FTO electro-conductive glass:
The FTO electro-conductive glass is placed the tubular heater heat treatment of annealing.Be warming up to 400 ℃-450 ℃ with 1-2 ℃/min speed, temperature retention time is 30-60mins, naturally cools to room temperature with stove.Template is set to hide the part that need not spray plated film at FTO conductive surface edge.
3) preparation of ZnO precursor polymer gel:
Hydrated salt (Zn (CH with zinc 3COO) 22H 2O, ZnSO 47H 2O or Zn (NO 3) 26H 2A kind of among the O), polymer (among PVAc, PVA or the PVP a kind of), solvent (one or both in DMF, deionized water or the ethanol) and catalyst (acetate; Add or do not add) drop in the beaker in ratio listed in the below table, or in the hydrated salt of zinc, further add dopant (Al (NO 3) 39H 2O, Al 2(SO 4) 3XH 2O, AlCl 36H 2A kind of among the O adds or do not add), be heated to 60 ℃; At rotating speed is under the 240-400r/min, and magnetic agitation 6hrs obtains even, transparent ZnO precursor polymer gel.ZnO precursor polymer gel forms according to the preparation of raw material of below table 1 parts by weight:
The raw material of table 1 ZnO precursor polymer gel is formed parts by weight (unit: gram)
Figure BDA0000072368810000081
Annotate: above-mentioned table 1 only is that the ZnO precursor polymer gel raw material that the present invention provides is formed preferred embodiment, be used for those skilled in the art and understand the present invention, but the present invention is not limited to the foregoing description.Below used ZnO precursor polymer gel all can make according to 8 embodiment of above-mentioned table 1 are selected.
4) structure of ZnO precursor polymer nanofiber membrane stress resilient coating
For improving ZnO precursor polymer nanofiber film and the relatively poor defective of electrically-conductive backing plate caking property, on the FTO electro-conductive glass, make up stress-buffer layer.
Use electric spinning device shown in Figure 1, the preparation nano-fiber film.To inject in the syringe pump as shown in Figure 1 through the ZnO precursor polymer gel that step 3) prepares, start the flow of syringe pump, will inject in gel force feed to the love dart stainless steel spinning head pin hole with 40-60 μ l/min; The stainless steel spinning head is connected with high voltage source, regulates high voltage source, and external loads voltage is 10-15kV; Control syringe pump flow keeps pin hole and grounding electrode to collect the substrate spacing at 10-15cm; Start electric spinning device, under electric field action, ZnO precursor polymer nanofiber is collected on the FTO electro-conductive glass of vertical syringe pump spinning head pin hole lower end, and forming thickness is the precursor polymer nanofiber film of 100-200nm; The pattern of ZnO precursor polymer nanofiber stress-buffer layer is as shown in Figure 2.
5) hot-pressing processing and the sintering of ZnO precursor polymer nanofiber membrane stress resilient coating
1. the hot-pressing processing of ZnO precursor polymer nanofiber film:
At first; The ZnO precursor polymer nanofiber film hot-pressing that adopts electric spining technology to make up is handled; The metal video disc that soon will be heated to 120-150 ℃ on the flattening oven places hot pressing 10-15mins on the ZnO precursor polymer nanofiber film, and the ptfe sheet that insertion 1-2mm is thick in the middle of metal video disc and ZnO precursor polymer nanofiber film is bonded on the metal fever video disc to stop nanofiber.
2. the sintering of ZnO precursor polymer nanofiber film:
Then, the ZnO precursor polymer nanofiber film after the hot-pressing processing at 80 ℃ of vacuumize 24hrs, with being placed on sintering furnace, is warming up to 400 ℃-450 ℃, temperature retention time is 30-60mins, removes organic substance, obtains the nano-fiber film stress-buffer layer.Sintering process is according to the rational temperature curve: promptly the speed with 1-2 ℃/min is warming up to 350 ℃, stops 10-15mins, is rapidly heated to 400 ℃-450 ℃ with 5 ℃/min of speed subsequently, and insulation 30-60mins naturally cools to room temperature with stove.Stress-buffer layer nano-fiber film microscopic appearance behind the sintering is as shown in Figure 3.
6) preparation of ZnO precursor polymer nanofiber film photoelectric electrode
For the proof stress resilient coating is improving nano-fiber film and electrically-conductive backing plate caking property role (being technique effect of the present invention), in the present embodiment, adopt two groups of different FTO electro-conductive glass to make up the optoelectronic pole of DSSC.One group of FTO electro-conductive glass makes up stress-buffer layer above that through electric spining technology, and does not make up stress-buffer layer on another group FTO electro-conductive glass.
The construction step of optoelectronic pole is following:
At first, adopt the ZnO precursor polymer gel solution of step 3) preparation on above-mentioned two groups of FTO electro-conductive glass, to adopt wet chemistry method (in hydro thermal method, sol-gal process or the electrical spinning method a kind of) to make up ZnO precursor polymer nanofiber.Adopt electric spining technology, construction step is identical with step 4).The pattern of the ZnO precursor polymer nanofiber film photoelectric electrode that makes up is as shown in Figure 4.
Subsequently, two groups of FTO substrates that are built with ZnO precursor polymer nanofiber film photoelectric electrode are placed the sintering furnace sintering, obtain the nano-fiber film optoelectronic pole of DSSC device.Sintering process is according to the rational temperature curve: promptly the speed with 1-2 ℃/min is warming up to 350 ℃, stops 10-15mins, is rapidly heated to 400 ℃-450 ℃ with 5 ℃/min of speed subsequently, and insulation 30-60mins naturally cools to room temperature with stove.
Optoelectronic pole behind the sintering such as Fig. 5, Fig. 6 and shown in Figure 7.For the optoelectronic pole that does not make up stress-buffer layer; Because the thermal coefficient of expansion of semiconductor nano fiber membrane and electrically-conductive backing plate is different; The elongation strain that sintering process produces often causes the contraction of the nano-fiber film on the electrically-conductive backing plate; Cause nano-fiber film cracking and fracture, or from electrically-conductive backing plate come off (like Fig. 5 and shown in Figure 6).And for the optoelectronic pole that makes up stress-buffer layer; Because resilient coating can effectively discharge the thermal stress at interface between semiconductor nano fiber membrane and the electrically-conductive backing plate; Stoped cracking, the fracture of nano-fiber film effectively and come off, made that the caking property between nano-fiber film and the electrically-conductive backing plate is improved well from electrically-conductive backing plate.ZnO nano-fiber film optoelectronic pole SEM pattern behind the sintering is as shown in Figure 7, and the pattern of nanofiber network structure can be by good maintenance.
Further the ZnO nano-fiber film optoelectronic pole behind the sintering being carried out hydrothermal solution handles; ZnO nano-fiber film optoelectronic pole is immersed in the zinc acetate aqueous solution of 0.1-0.3M and keeps 5-15mins; Then set by step 6) optoelectronic pole of the sintering curre in after the sintering hydrothermal solution is handled once more, the micro-crack on optoelectronic pole surface can be repaired well.
7) structure of nano-fiber film DSSC
Make up battery according to M.
Figure BDA0000072368810000111
the invention construction method that dye sensitized nano crystal salar battery adopted, as shown in Figure 8.At first, adopt N3 or N719 dyestuff that two groups of ZnO nano-fiber film optoelectronic poles of step 6) preparation are carried out sensitization; Subsequently, the with holes of platinumization carried out encapsulation process to electrode and work electrode; Utilize the capillary absorption principle to inject the electrolyte that contains iodide ion again; Finally sealed obtains DSSC DSSC device to being used to inject the aperture of electrolyte on the electrode.
8) structure of DSSC and performance test
The performance that adopts the solar energy analogue means to test two Battery packs, test result is as shown in Figure 9, and the structure of stress-buffer layer has improved the open circuit photovoltage and the photovoltaic energy conversion efficient of DSSC device greatly, has improved the performance of DSSC significantly.
Above-mentionedly provided that the embodiment of the present invention method prepares the practical implementation step of DSSC DSSC device and to structure and the performance test step thereof of DSSC device.Optoelectronic pole (Fig. 5, Fig. 6 and shown in Figure 7) through behind the contrast sintering can be known; The structure of stress-buffer layer of the present invention; Cracking and the fracture and the coming off from the electrically-conductive backing plate that can stop optoelectronic pole nano-fiber film in the sintering process effectively make the network configuration pattern of nanofiber optoelectronic pole keep good.In addition, electric spinning treatment technology and hot-pressing processing, operation is simple, and strong with optoelectronic pole preparation technology compatibility, and treatment effect is good.Utilize the method and technology, optoelectronic pole is effectively protected, battery performance be greatly improved (photovoltaic energy conversion efficient is increased to 0.55% from 0.04%).The optoelectronic pole material property is stable, has guaranteed the stable, reliable of battery performance, has reached practical and long-life purpose.
Below table 2 has provided the embodiment of the used technical measures different technologies of embodiment of the present invention parameter.Every parameter of in table 2, not listing is all implemented with reference to the foregoing description parameter.Everyly in the inventive method step relate to the situation that parameter is a point, all implement according to the given step of practical implementation step among the embodiment.
The parameter area of the used technical measures of table 2 the present invention
Annotate: listed each parameter area of table 2 relates to the selected embodiment of parameter area for the inventive method step, and the listed parameter area of table 2 is applicable among 8 embodiment of above-mentioned table 1 respectively.
The above; Only be to the present invention is directed to the embodiment that the present invention improves the close-burning method of DSSC substrate interface; The foregoing description is not that the present invention is done any restriction; Every according to the present invention the given scope of technical scheme and any simple modification, change and equivalent structure that above embodiment did changed, all still belong to the protection range of technical scheme of the present invention.
It is pointed out that according to technical scheme of the present invention, the foregoing description can also be enumerated many, prove,, all can reach the object of the invention in the scope that claims of the present invention proposed according to applicant's lot of experiment results.

Claims (6)

1. one kind is improved the close-burning method of DSSC substrate interface, it is characterized in that this method may further comprise the steps:
1) clean of FTO electro-conductive glass
The FTO electro-conductive glass is cleaned 3 times with isopropyl acetone, alcohol and deionized water successively repeatedly, and each scavenging period is 10mins, then with the hot-air behind the filtration, purification at the hothouse inner drying;
2) annealing in process of FTO electro-conductive glass
The FTO electro-conductive glass is placed the tubular heater heat treatment of annealing, be warming up to 400 ° of C-450 ° of C with 1-2 ° of C/min speed, temperature retention time is 30-60mins, naturally cools to room temperature with stove;
3) preparation of ZnO precursor polymer gel
Hydrated salt, polymer, solvent and the catalyst of zinc are dropped in the beaker by a certain percentage, be heated to 60 ° of C; At rotating speed is under the 240-400r/min, and magnetic agitation 6hrs obtains even, transparent ZnO precursor polymer gel;
4) structure of ZnO precursor polymer nanofiber membrane stress resilient coating
The ZnO precursor polymer gel of preparation is injected syringe; Send in the stainless steel spinning head pin hole with the flow of 40-60 μ l/min through syringe pump; The stainless steel spinning head is connected with high voltage source; External loads voltage is 10-15kV, keeps stainless steel spinning head pin hole and grounding electrode to collect the substrate spacing at 10-15cm; Start electric spinning device, under electric field action, ZnO precursor polymer nanofiber is collected on the FTO electro-conductive glass of vertical syringe pump spinning head pin hole lower end, and forming thickness is the precursor polymer stress-buffer layer nano-fiber film of 100-200nm;
5) ZnO precursor polymer nanofiber membrane stress resilient coating hot-pressing processing and sintering
1. ZnO precursor polymer nanofiber film hot-pressing is handled: the metal video disc that is heated to 120 ° of C-150 ° of C on the flattening oven is placed hot pressing 10-15mins on the ZnO precursor polymer nanofiber film, and in the middle of metal video disc and ZnO precursor polymer nanofiber film, insert the thick ptfe sheet of 1-2mm;
2. ZnO precursor polymer nanofiber is film sintered: the ZnO precursor polymer nanofiber film after the hot-pressing processing is at 80 ° of C vacuumize 24hrs; Place sintering furnace then; Be warming up to 400 ° of C-450 ° of C; Temperature retention time is 30-60mins, naturally cools to room temperature with stove, obtains ZnO precursor polymer nanofiber membrane stress resilient coating;
6) preparation of ZnO precursor polymer nanofiber film photoelectric electrode
On the FTO electro-conductive glass that applies ZnO precursor polymer nanofiber membrane stress resilient coating, adopt wet chemistry method to make up conductor oxidate ZnO film work electrode; Place sintering furnace then; Be warming up to 400 ° of C-450 ° of C sintering; Temperature retention time is 30-60mins, naturally cools to room temperature with stove, obtains the ZnO nano-fiber film optoelectronic pole of DSSC device;
7) structure of nano-fiber film DSSC
Adopt N3 or N719 dyestuff that the ZnO nano-fiber film optoelectronic pole of preparation is carried out sensitization; Subsequently the with holes of platinumization carried out encapsulation process to the ZnO nano-fiber film optoelectronic pole after electrode and the sensitization; Utilize the capillary absorption principle to inject the electrolyte that contains iodide ion; Finally sealed obtains DSSC DSSC device to being used to inject the aperture of electrolyte on the electrode.
2. a kind of close-burning method of DSSC substrate interface of improving according to claim 1 is characterized in that said ZnO precursor polymer gel is formulated according to following materials based on weight:
Zinc hydrated salt 0.5-10 part;
Polymer 0.2-7 part;
Solvent 10-47 part;
Catalyst 0-4 part;
The hydrated salt of said zinc is hydration zinc acetate Zn (CH 3COO) 22H 2O, zinc sulphate hydrate ZnSO 47H 2O or nitric hydrate zinc Zn (NO 3) 26H 2A kind of among the O, purity is greater than 99.99%;
Said polymer is a kind of among polyvinyl acetate PVAc, PVAC polyvinylalcohol or the PVP PVP;
Said solvent is one or both in dimethyl formamide DMF, deionized water or the ethanol;
Said catalyst is an acetate.
3. a kind of close-burning method of DSSC substrate interface of improving according to claim 2 is characterized in that the hydrated salt of said zinc further adds dopant, and dopant is the hydrated sulfate Al of aluminium 2(SO 4) 3XH 2O, nitric hydrate salt Al (NO 3) 39H 2O or hydration halide salt AlCl 36H 2A kind of among the O, its purity is higher than 99.99%; The addition of dopant adds according to the atomic percentage conc 0-6atom% of doped with Al element in ZnO.
4. a kind of close-burning method of DSSC substrate interface of improving according to claim 1; It is characterized in that; In the said step 6); Further ZnO nano-fiber film optoelectronic pole is carried out hydrothermal solution and handle, ZnO nano-fiber film optoelectronic pole is immersed in the zinc acetate aqueous solution of 0.1-0.3M and keeps 5-15mins, and then the optoelectronic pole of sintering hydrothermal solution after handling.
5. according to the said a kind of close-burning method of DSSC substrate interface of improving of claim 1; It is characterized in that; Sintering is characterized as in said step 5), the step 6): the speed with 1-2 ° of C/min is warming up to 350 ° of C; Stop 10-15mins, be rapidly heated to 400 ° of C-450 ° of C with 5 ° of C/min of speed subsequently, insulation 30-60mins.
6. according to the said a kind of close-burning method of DSSC substrate interface of improving of claim 1, it is characterized in that wet chemistry method is a kind of of hydro thermal method, sol-gal process or electrical spinning method in the said step 6).
CN 201110179968 2011-06-29 2011-06-29 Method for improving interface caking property of dye sensitized solar cell substrate Active CN102324308B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 201110179968 CN102324308B (en) 2011-06-29 2011-06-29 Method for improving interface caking property of dye sensitized solar cell substrate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 201110179968 CN102324308B (en) 2011-06-29 2011-06-29 Method for improving interface caking property of dye sensitized solar cell substrate

Publications (2)

Publication Number Publication Date
CN102324308A CN102324308A (en) 2012-01-18
CN102324308B true CN102324308B (en) 2012-10-17

Family

ID=45452028

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 201110179968 Active CN102324308B (en) 2011-06-29 2011-06-29 Method for improving interface caking property of dye sensitized solar cell substrate

Country Status (1)

Country Link
CN (1) CN102324308B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101540234A (en) * 2008-03-20 2009-09-23 东进世美肯株式会社 Method of producing dye sensitization solar cell
CN101889366A (en) * 2008-10-09 2010-11-17 索尼公司 Functional device and manufacturing method therefor

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101540234A (en) * 2008-03-20 2009-09-23 东进世美肯株式会社 Method of producing dye sensitization solar cell
CN101889366A (en) * 2008-10-09 2010-11-17 索尼公司 Functional device and manufacturing method therefor

Also Published As

Publication number Publication date
CN102324308A (en) 2012-01-18

Similar Documents

Publication Publication Date Title
CN101702377B (en) Zinc oxide/titanium dioxide hybrid electrode and preparation method thereof
CN104157788B (en) It is a kind of to be based on SnO2Perovskite thin film photovoltaic cell and preparation method thereof
CN107359248B (en) A kind of stabilization is without efficient organic solar batteries device of light bath and preparation method thereof
CN104900809B (en) Carbon counter electrode perovskite solar cell and manufacturing method thereof
CN104966763B (en) Method of improving efficiency of perovskite solar cell
CN106128772B (en) A kind of preparation method of vulcanized lead quantum dot photovoltaic battery
CN101162739B (en) ZnO electrode of dye sensitization solar cell and method for producing the same
CN104952963A (en) Method for preparing TiO2-ZnO hetero-junction nanorod for perovskite solar cell
CN109768167A (en) The perovskite solar cell and preparation method thereof of no current sluggishness
CN106299141A (en) A kind of manufacture method of the perovskite solaode of composite electron transport layer structure
CN108281550A (en) Based on the titania-doped perovskite solar cell and preparation method thereof of magnesium
CN101872685B (en) Solid dye-sensitized nanocrystal/microcrystal silicon composite film solar cell and preparation method thereof
CN109585054A (en) The dry conductive carbon paste of green solvent Shift Method is applied to perovskite solar battery
CN108492993A (en) A kind of noble metal decorated TiO2-BaTiO3Core-shell nano linear array complex light anode and preparation method
CN102222575A (en) Preparation method for photoanode of dye-sensitized solar cell
CN103456511A (en) Post-embedding method for preparing ZnO nanorod/TiO2 nano-particle composite film
CN103236352A (en) Preparation method of ZnO sol compounded Sn doping ZnO thick films
CN102324308B (en) Method for improving interface caking property of dye sensitized solar cell substrate
CN101814376A (en) ZnO composite electrode of dye-sensitized solar battery and preparation method thereof
CN112614942B (en) PEG-modified carbon electrode, preparation method thereof and perovskite battery prepared by using PEG-modified carbon electrode
CN105280389A (en) Preparation method for dye-sensitized solar cell
CN102683032B (en) Preparation of foliated titanium dioxide nano array thin film electrode and application of foliated titanium dioxide nano array thin film electrode in dye sensitized solar cell
CN110359058B (en) Preparation method of lead zirconate titanate modified hematite nanorod array photoanode
CN107369729B (en) A kind of nano ordered interpenetrating total oxygen compound hetero-junction thin-film solar cell and preparation method thereof
CN103578775B (en) Based on the dye-sensitized solar cells and preparation method thereof of ZnO transparent conductive nanowire array electrode

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant