CN105225839A - A kind of preparation method of high efficiency zno-based dye-sensitized solar cell anode and obtained light anode thereof - Google Patents
A kind of preparation method of high efficiency zno-based dye-sensitized solar cell anode and obtained light anode thereof Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of high efficiency zno-based dye-sensitized solar cell anode, after configuring ZnO colloidal sol, utilize ZnO colloidal sol first making ZnO dense barrier layer in conductive substrates; Then chemical bath growth method is adopted, using six water nitrate and aqueous solution of urea as growth-promoting media, first carry out growth-promoting media preheating by sectional temperature control, then carry out the mode of growth response, conductive substrates is prepared the zno-based nanometer sheet dye-sensitized solar cell anode film of Large-Area-Uniform densification.In addition, the light anode utilizing above-mentioned preparation method to obtain is also disclosed.The present invention is micron dimension by obtaining standing upright height in conductive substrates, has the ZnO nano sheet of two kinds of pore structures, prepare Large-Area-Uniform, arrange ZnO nano sheet film closely, efficiently solve the slow and problem of electron recombination of current zno-based dye-sensitized solar cell anode electric transmission, obtain higher photoelectric conversion efficiency.
Description
Technical field
The present invention relates to energy technology field, particularly relate to a kind of preparation method of DSSC zno-based light anode and obtained light anode thereof.
Background technology
Energy problem governs expanding economy, solar energy as inexhaustible, environmental protection the energy and receive much concern.Current investigation and application is solar cell mainly silicon system solar cell the most widely, but to problems such as environments, thus can limit its extensive use because its cost is high, in large, the production process of complex process, energy consumption.1991,
deng assembling the DSSC (DyeSensitizedSolarCell is called for short DSSC) that photoelectric conversion efficiency reaches 7.9% first, start the uncharted field of solar cell research and development.DSSC is by light anode, form a few parts such as electrode, dye sensitizing agent, conductive substrates, electrolyte, and wherein light anode is the core component of DSSC.Nano ZnO material, owing to having band structure and other parts of DSSC match, conductivity is high, be easy to the features such as film formation at low temp and pattern be abundant, becomes a kind of important DSSC light anode material.But at present zno-based light anode also exists the slow and problem of electron recombination of electric transmission, thus causes zno-based DSSC battery efficiency low, and its reason is mainly: the carboxyl reaction one, in ZnO and dyestuff N719 and N3 forms Zn
2+/ dye complexes, Zn
2+/ dye complexes can be grown up rapidly, between the hole being distributed in ZnO film and on the surface, works as Zn
2+after dye absorber photon in/dye complexes, excitation electron cannot be diffused into surface, but cancellation in the polymer, thus cause the electron injection rate of zno-based light anode low; Two, current ZnO photo-anode Design of Membrane Structure is unreasonable, and existing ZnO nanorod, ZnO nanotube/and ZnO nano are assembled the light anodes such as ball and be there is the shortcoming that specific area is little and light induced electron compound is fast.Therefore, the dyestuff that the acidity of the applicable zno-based of exploitation is more weak and the novel ZnO photo-anode structure of design just become the focus of current research.The ZnO nano sheet of vertical conduction substrate is the potential smooth anode of a kind of tool, but the preparation method of current this smooth anode all also exists that prepared film is uneven and nanometer sheet arranges sparse shortcoming in conductive substrates; Meanwhile, the nanometer sheet near conductive substrates is not vertical conduction substrate, but has certain inclination, and photoelectric conversion efficiency is still undesirable.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of high efficiency zno-based dye-sensitized solar cell anode is provided, be micron dimension by obtaining standing upright height in conductive substrates, there is the ZnO nano sheet of two kinds of pore structures (micropore and mesoporous), prepare Large-Area-Uniform, arrange ZnO nano sheet film closely, to solve the slow and problem of electron recombination of current zno-based dye-sensitized solar cell anode electric transmission.Another object of the present invention is to provide the light obtained by above-mentioned preparation method anode.
Object of the present invention is achieved by the following technical programs:
The preparation method of a kind of high efficiency zno-based dye-sensitized solar cell anode provided by the invention is as follows: after configuring ZnO colloidal sol, utilizes described ZnO colloidal sol first making ZnO dense barrier layer in conductive substrates; Then chemical bath growth method is adopted, using six water nitrate and aqueous solution of urea as growth-promoting media, first carry out growth-promoting media preheating by sectional temperature control, then carry out the mode of growth response, described conductive substrates is prepared the zno-based nanometer sheet dye-sensitized solar cell anode film of Large-Area-Uniform densification.
The present invention, by preparation coating ZnO dense barrier layer in conductive substrates, decreases the roughness on conductive base counterdie surface, makes the zno-based nanometer sheet near conductive substrates bottom film finer and close, vertical.Adopt the mode of sectional temperature control, the urea decomposition in growth-promoting media can be made by preheating, make the pH value of growth-promoting media system be increased to about 6.5 by about 5, thus avoid the dissolving of the ZnO film generated the earliest (ZnO is amphoteric oxide, non-acid resistance); Meanwhile, the pre-thermal decomposition of urea can discharge NH in advance
3and CO
2gas, prevent gas from producing when growth response and be attached to conductive substrates surface and then cause film to occur pore, the film that the generation due to pore can be avoided to cause is uneven, thus can obtain the photo-anode film of Large-Area-Uniform.
The present invention can take following concrete measure further:
The preparation method of high efficiency zno-based dye-sensitized solar cell anode of the present invention, comprises the following steps:
(1) preparation of ZnO colloidal sol
Two water zinc acetates and monoethanolamine or diethanol amine are dissolved in making ZnO colloidal sol in EGME solution;
(2) preparation of ZnO dense barrier layer
Adopt stain leaching method, make conductive substrates apply ZnO colloidal sol; Then the conductive substrates scribbling ZnO colloidal sol is dried, calcined, thus obtain ZnO dense barrier layer in conductive substrates coating;
(3) preparation of the ZnO nano sheet film of vertical conduction substrate
(3-1) preparation of growth-promoting media
Using the mixed liquor of zinc nitrate hexahydrate and aqueous solution of urea as the growth-promoting media of chemical bath, described growth-promoting media is carried out be preheated to solution turned cloudy and start to occur crystallization;
(3-2) preparation of ZnO nano sheet film
By the described conductive substrates being coated with ZnO dense barrier layer, the growth-promoting media after putting into described preheating down with aufwuchsplate carries out growth response; Through rinsing, drying, calcine after reaction terminates, i.e. obtained zno-based nanometer sheet dye-sensitized solar cell anode.
In such scheme, for removing the gas that the pre-thermal decomposition of urea produces further, in step of the present invention (3-1) after growth-promoting media preheating, adopting in ultrasonic process to solution and there is no bubble.
Further, in step of the present invention (1), two water zinc acetates and monoethanolamine or the concentration of diethanol amine in EGME solution are respectively 0.20 ~ 0.60M.
Further, the bake out temperature scribbling the conductive substrates of ZnO colloidal sol in step of the present invention (2) is 60 ~ 120 DEG C, and calcining heat is 250 ~ 500 DEG C, and temperature retention time is 30 ~ 120min.
Further, the concentration of zinc nitrate hexahydrate in growth-promoting media in step of the present invention (3-1) is 0.15 ~ 0.60M; The concentration of urea in growth-promoting media is 1.70 ~ 4.00M.
Further, in step of the present invention (3-1), the preheat temperature of growth-promoting media is 60 ~ 90 DEG C, and warm-up time is 1 ~ 6h.
Further, in step of the present invention (3-2), the temperature of growth response is 60 ~ 90 DEG C, and the reaction time is 2 ~ 6h.
Further, in step of the present invention (3-2), bake out temperature is 60 ~ 120 DEG C; Calcining heat 250 ~ 450 DEG C.
Another object of the present invention is achieved by the following technical programs:
Utilize the light anode that above-mentioned preparation method obtains, described smooth anode is by ZnO dense barrier layer and have micropore and mesoporous ZnO nano sheet film forms; Described ZnO dense barrier layer is coated in conductive substrates; Described ZnO nano sheet standing upright is on ZnO dense barrier layer, and it is highly micron dimension, it is furnished with mesoporous; Interlaced, stacking and form micropore between described ZnO nano sheet.
The present invention has following beneficial effect:
(1) first preparation method of the present invention applies ZnO dense barrier layer in conductive substrates, decrease the roughness on conductive base counterdie surface, make the zno-based nanometer sheet near conductive substrates bottom film finer and close, compare the nanometer sheet film more vertical conduction substrate obtained when not having ZnO dense barrier layer, nanometer sheet arrangement simultaneously closely.
(2) the present invention adopts chemical baths, by the mode of sectional temperature control, before growth response, carries out preheating to growth-promoting media, makes the urea decomposition in growth-promoting media, improves growth-promoting media system pH and decompose to discharge NH
3and CO
2gas, is not only beneficial to the growth of nanometer sheet, and film can be avoided to occur pore, thus the photo-anode film of obtained Large-Area-Uniform.
(3) the ZnO nano sheet film that the light anode that obtains of the present invention is micron dimension by the height of ZnO dense barrier layer and standing upright forms.And there are two kinds of pore structures in this ZnO nano sheet film simultaneously: a kind of is the micropore of interlaced between nanometer sheet and nanometer sheet, stacking formation; Another kind is that it is mesoporous to be clouded in nanometer sheet.This structure of ZnO nano sheet film of the present invention is as the advantage of DSSC work electrode: a. is relative to three-dimensional disordered networks structure, in ZnO meso-porous nano chip architecture, light induced electron can to go directly conductive substrates along two-dimensional nano sheet, improves the collection efficiency of light induced electron; The mesoporous specific area substantially increasing nanometer sheet of b. gathering, thus increase Dye Adsorption amount and photogenerated current; C. between nanometer sheet, electrolyte infiltration is convenient in micron-sized space.Therefore, the ZnO nano sheet of double pores system of the present invention is conducive to the transmission at light anode/dyestuff/electrolyte interface of the absorption of dyestuff, the infiltration of electrolyte and electronics, thus obtains higher photoelectric conversion efficiency.
Accompanying drawing explanation
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail:
Fig. 1 is the SEM figure of various embodiments of the present invention and the photo-anode film obtained by comparative example;
Fig. 2 is SEM figure (multiplication factor) of the photo-anode film obtained by the embodiment of the present invention five.
Embodiment
The preparation method of embodiment of the present invention high efficiency zno-based dye-sensitized solar cell anode, adopts the fin oxide condutire glass mixing fluorine as conductive substrates, after configuring ZnO colloidal sol, utilizes ZnO colloidal sol first making ZnO dense barrier layer in conductive substrates; Then chemical bath growth method is adopted, using six water nitrate and aqueous solution of urea as growth-promoting media, first carry out growth-promoting media preheating by sectional temperature control, then carry out the mode of growth response, thus in conductive substrates, prepare the zno-based nanometer sheet dye-sensitized solar cell anode film of Large-Area-Uniform densification.Specific as follows:
Embodiment one:
The preparation method of the present embodiment high efficiency zno-based dye-sensitized solar cell anode, its step is as follows:
(1) preparation of ZnO colloidal sol
50ml EGME solution is placed on magnetic stirring apparatus and stirs, and add 4.39g bis-water zinc acetate and 1.20ml monoethanolamine when stirring, at 25 DEG C of temperature, stir 10h, namely obtained transparent ZnO colloidal sol; Two water zinc acetates and the concentration of monoethanolamine in EGME solution are 0.4M;
(2) preparation of ZnO dense barrier layer
Adopt stain leaching method, the conductive substrates cleaned up be immersed in above-mentioned ZnO colloidal sol, after 4s, average rate proposes conductive substrates; The conductive substrates scribbling ZnO colloidal sol dried at 60 DEG C of temperature in program heating and cooling baking oven, then calcine in Muffle furnace, calcining heat is 450 DEG C, and temperature retention time is 30min, thus obtains ZnO dense barrier layer in conductive substrates coating; Wherein, the heating rate of oven dry and calcining is 8 DEG C/min;
(3) preparation of the ZnO nano sheet film of vertical conduction substrate
(3-1) preparation of growth-promoting media
First the deionized water measuring 300mL is poured in the beaker of 400mL, when magnetic agitation, adds 13.38g zinc nitrate hexahydrate and the dissolving of 60g urea successively, stirred by solution, obtain growth-promoting media to beaker; Wherein, the concentration of zinc nitrate hexahydrate in growth-promoting media is 0.15M, and the concentration of urea in growth-promoting media is 3.33M; Then will fill the beaker sealing of growth-promoting media, put into program heating and cooling baking oven, preheating 6h at 60 DEG C of temperature, starts to occur crystallization to solution turned cloudy; Afterwards, ultrasonic cleaning machine ultrasonic process 1min is adopted to make do not have bubble in solution;
(3-2) preparation of ZnO nano sheet film
To the conductive substrates of ZnO dense barrier layer be coated with, put into the beaker filling growth-promoting media with aufwuchsplate down, then program heating and cooling baking oven is put in beaker sealing, at 90 DEG C of temperature, react 2h; Reaction terminates rear taking-up, with deionized water rinsing, dries at 100 DEG C, and then at 350 DEG C of temperature lower calcinations, insulation 30min, the heating rate wherein dried and calcine is 8 DEG C/min, i.e. obtained zno-based dye-sensitized solar cell anode film.
Embodiment two:
The preparation method of the present embodiment high efficiency zno-based dye-sensitized solar cell anode, its step is as follows:
(1) preparation of ZnO colloidal sol
50ml EGME solution is placed on magnetic stirring apparatus and stirs, and add 4.39g bis-water zinc acetate and 1.20ml monoethanolamine when stirring, at 25 DEG C of temperature, stir 10h, namely obtained transparent ZnO colloidal sol; Two water zinc acetates and the concentration of monoethanolamine in EGME solution are 0.4M;
(2) preparation of ZnO dense barrier layer
Adopt stain leaching method, the conductive substrates cleaned up be immersed in above-mentioned ZnO colloidal sol, after 4s, average rate proposes conductive substrates; The conductive substrates scribbling ZnO colloidal sol dried at 60 DEG C of temperature in program heating and cooling baking oven, then calcine in Muffle furnace, calcining heat is 450 DEG C, and temperature retention time is 30min, thus obtains ZnO dense barrier layer in conductive substrates coating; Wherein, the heating rate of oven dry and calcining is 8 DEG C/min;
(3) preparation of the ZnO nano sheet film of vertical conduction substrate
(3-1) preparation of growth-promoting media
First the deionized water measuring 300mL is poured in the beaker of 400mL, when magnetic agitation, adds 26.77g zinc nitrate hexahydrate and the dissolving of 40g urea successively, stirred by solution, obtain growth-promoting media to beaker; Wherein, the concentration of zinc nitrate hexahydrate in growth-promoting media is 0.30M, and the concentration of urea in growth-promoting media is 2.20M; Then will fill the beaker sealing of growth-promoting media, put into program heating and cooling baking oven, preheating 3h at 60 DEG C of temperature, starts to occur crystallization to solution turned cloudy; Afterwards, ultrasonic cleaning machine ultrasonic process 1min is adopted to make do not have bubble in solution;
(3-2) preparation of ZnO nano sheet film
To the conductive substrates of ZnO dense barrier layer be coated with, put into the beaker filling growth-promoting media with aufwuchsplate down, then program heating and cooling baking oven is put in beaker sealing, at 80 DEG C of temperature, react 4h; Reaction terminates rear taking-up, with deionized water rinsing, dries at 100 DEG C, and then at 350 DEG C of temperature lower calcinations, insulation 30min, the heating rate wherein dried and calcine is 8 DEG C/min, i.e. obtained zno-based dye-sensitized solar cell anode film.
Embodiment three:
(1) preparation of ZnO colloidal sol
50ml EGME solution is placed on magnetic stirring apparatus and stirs, and add 4.39g bis-water zinc acetate and 1.20ml monoethanolamine when stirring, at 25 DEG C of temperature, stir 10h, namely obtained transparent ZnO colloidal sol; Two water zinc acetates and the concentration of monoethanolamine in EGME solution are 0.4M;
(2) preparation of ZnO dense barrier layer
Adopt stain leaching method, the conductive substrates cleaned up be immersed in above-mentioned ZnO colloidal sol, after 4s, average rate proposes conductive substrates; The conductive substrates scribbling ZnO colloidal sol dried at 60 DEG C of temperature in program heating and cooling baking oven, then calcine in Muffle furnace, calcining heat is 450 DEG C, and temperature retention time is 30min, thus obtains ZnO dense barrier layer in conductive substrates coating; Wherein, the heating rate of oven dry and calcining is 8 DEG C/min;
(3) preparation of the ZnO nano sheet film of vertical conduction substrate
(3-1) preparation of growth-promoting media
First the deionized water measuring 300mL is poured in the beaker of 400mL, when magnetic agitation, adds 26.77g zinc nitrate hexahydrate and the dissolving of 60g urea successively, stirred by solution, obtain growth-promoting media to beaker; Wherein, the concentration of zinc nitrate hexahydrate in growth-promoting media is 0.30M, and the concentration of urea in growth-promoting media is 3.33M; Then will fill the beaker sealing of growth-promoting media, put into program heating and cooling baking oven, preheating 1h at 90 DEG C of temperature, starts to occur crystallization to solution turned cloudy; Afterwards, ultrasonic cleaning machine ultrasonic process 1min is adopted to make do not have bubble in solution;
(3-2) preparation of ZnO nano sheet film
To the conductive substrates of ZnO dense barrier layer be coated with, put into the beaker filling growth-promoting media with aufwuchsplate down, then program heating and cooling baking oven is put in beaker sealing, at 90 DEG C of temperature, react 2h; Reaction terminates rear taking-up, with deionized water rinsing, dries at 100 DEG C, and then at 450 DEG C of temperature lower calcinations, insulation 30min, the heating rate wherein dried and calcine is 8 DEG C/min, i.e. obtained zno-based dye-sensitized solar cell anode film.
Embodiment four:
The preparation method of the present embodiment high efficiency zno-based dye-sensitized solar cell anode, its step is as follows:
(1) preparation of ZnO colloidal sol
50ml EGME solution is placed on magnetic stirring apparatus and stirs, and add 3.29g bis-water zinc acetate and 1.44ml diethanol amine when stirring, at 25 DEG C of temperature, stir 10h, namely obtained transparent ZnO colloidal sol; Two water zinc acetates and the concentration of diethanol amine in EGME solution are 0.3M;
(2) preparation of ZnO dense barrier layer
Adopt stain leaching method, the conductive substrates cleaned up be immersed in above-mentioned ZnO colloidal sol, after 4s, average rate proposes conductive substrates; The conductive substrates scribbling ZnO colloidal sol dried at 60 DEG C of temperature in program heating and cooling baking oven, then calcine in Muffle furnace, calcining heat is 500 DEG C, and temperature retention time is 30min, thus obtains ZnO dense barrier layer in conductive substrates coating; Wherein, the heating rate of oven dry and calcining is 8 DEG C/min;
(3) preparation of the ZnO nano sheet film of vertical conduction substrate
(3-1) preparation of growth-promoting media
First the deionized water measuring 300mL is poured in the beaker of 400mL, when magnetic agitation, adds 13.38g zinc nitrate hexahydrate and the dissolving of 60g urea successively, stirred by solution, obtain growth-promoting media to beaker; Wherein, the concentration of zinc nitrate hexahydrate in growth-promoting media is 0.15M, and the concentration of urea in growth-promoting media is 3.33M; Then will fill the beaker sealing of growth-promoting media, put into program heating and cooling baking oven, preheating 4h at 60 DEG C of temperature, starts to occur crystallization to solution turned cloudy; Afterwards, ultrasonic cleaning machine ultrasonic process 1min is adopted to make do not have bubble in solution;
(3-2) preparation of ZnO nano sheet film
To the conductive substrates of ZnO dense barrier layer be coated with, put into the beaker filling growth-promoting media with aufwuchsplate down, then program heating and cooling baking oven is put in beaker sealing, at 90 DEG C of temperature, react 4h; Reaction terminates rear taking-up, with deionized water rinsing, dries at 100 DEG C, and then at 450 DEG C of temperature lower calcinations, insulation 30min, the heating rate wherein dried and calcine is 8 DEG C/min, i.e. obtained zno-based dye-sensitized solar cell anode film.
Embodiment five:
The preparation method of the present embodiment high efficiency zno-based dye-sensitized solar cell anode, its step is as follows:
(1) preparation of ZnO colloidal sol
50ml EGME solution is placed on magnetic stirring apparatus and stirs, and add 3.29g bis-water zinc acetate and 1.44ml diethanol amine when stirring, at 25 DEG C of temperature, stir 10h, namely obtained transparent ZnO colloidal sol; The concentration of two water zinc acetates and diethanol amine is 0.3M;
(2) preparation of ZnO dense barrier layer
Adopt stain leaching method, the conductive substrates cleaned up be immersed in above-mentioned ZnO colloidal sol, after 4s, average rate proposes conductive substrates; The conductive substrates scribbling ZnO colloidal sol dried at 60 DEG C of temperature in program heating and cooling baking oven, then calcine in Muffle furnace, calcining heat is 500 DEG C, and temperature retention time is 30min, thus obtains ZnO dense barrier layer in conductive substrates coating; Wherein, the heating rate of oven dry and calcining is 8 DEG C/min;
(3) preparation of the ZnO nano sheet film of vertical conduction substrate
(3-1) preparation of growth-promoting media
First the deionized water measuring 300mL is poured in the beaker of 400mL, when magnetic agitation, adds 13.38g zinc nitrate hexahydrate and the dissolving of 60g urea successively, stirred by solution, obtain growth-promoting media to beaker; Wherein, the concentration of zinc nitrate hexahydrate in growth-promoting media is 0.15M, and the concentration of urea in growth-promoting media is 3.33M; Then will fill the beaker sealing of growth-promoting media, put into program heating and cooling baking oven, preheating 4h at 60 DEG C of temperature, starts to occur crystallization to solution turned cloudy; Afterwards, ultrasonic cleaning machine ultrasonic process 1min is adopted to make do not have bubble in solution;
(3-2) preparation of ZnO nano sheet film
To the conductive substrates of ZnO dense barrier layer be coated with, put into the beaker filling growth-promoting media with aufwuchsplate down, then program heating and cooling baking oven is put in beaker sealing, at 90 DEG C of temperature, react 4h; Reaction terminates rear taking-up, with deionized water rinsing, dries at 100 DEG C, and then at 350 DEG C of temperature lower calcinations, insulation 30min, the heating rate wherein dried and calcine is 8 DEG C/min, i.e. obtained zno-based dye-sensitized solar cell anode film.
Comparative example:
Comparative example and embodiment four difference are:
1, comparative example is without the step (1) of embodiment four, (2), and namely comparative example does not have the preparation of ZnO colloidal sol, and its conductive substrates does not apply ZnO dense barrier layer;
2, comparative example is without the preheating treatment procedure of embodiment four step (3-1) growth-promoting media, and namely comparative example is that directly conductive substrates is put into growth-promoting media carries out growth response.
As shown in Figure 1, compared with comparative example, the ZnO nano sheet more vertical conduction substrate of the light anode prepared by the embodiment of the present invention, and arrange more tight between nanometer sheet, thus be conducive to the raising of battery efficiency.
Light anode obtained by the embodiment of the present invention is by ZnO dense barrier layer and have micropore and mesoporous ZnO nano sheet film forms.Wherein, ZnO dense barrier layer is coated in conductive substrates; ZnO nano sheet standing upright is on ZnO dense barrier layer, and it is highly micron dimension, it is furnished with mesoporous (see Fig. 2); Interlaced between ZnO nano sheet, stacking and form micropore.
The light anode adopting the embodiment of the present invention and comparative example to obtain, make DSSC in accordance with the following methods:
The ZnO photo-anode film of 80 DEG C will be cooled to after calcining, under room temperature, 24h is flooded in 0.05mMN719 dyestuff, take out the N719 dyestuff that photo-anode film absolute ethyl alcohol rinses surface, then adsorb the photo-anode film of N719 dyestuff and the FTO of pyrolysis platinum forms open sandwich structure battery to electrode by after oven dry.Light anode and to electrode between drip electrolyte, the acetonitrile solution consisting of 0.6M1-butyl-3-methylimidazole salt compounded of iodine, 0.06MLiI, 0.03MI2,0.5M4-tert .-butylpyridine and 0.1M guanidinium isothiocyanate of liquid electrolyte, solid electrolyte consist of PEO based polyalcohol colloidal electrolyte: 0.1MLiI, 0.1MI2,0.6M1,2-dimethyl-3-propyl imidazole iodine, 0.45MN-methyl-benzoimidazole, the polyethylene glycol oxide (PEO) of solvent to be 3-methoxypropionitrile (MePN) and weight be 7.5% of above electrolyte gross mass.
The photoelectric properties parameter of obtained DSSC is as shown in table 1.
Table 1 embodiment of the present invention and comparative example DSSC photoelectric properties parameter
Compared with comparative example, its transformation efficiency of DSSC PCE obtained by embodiment of the present invention light anode, open circuit voltage Voc, short circuit current Jsc and fill factor, curve factor FF have greatly improved, its reason is: what the embodiment of the present invention obtained is more upright ZnO nano sheet, and nanometer sheet arrangement is more tight, therefore the compound of light induced electron is few, thus makes properties all have lifting.Meanwhile, because ZnO can be corroded from an electrolyte in liquid electrolyte, and corrosivity reduces in solid electrolyte, and therefore, the performance of the present invention's ZnO battery in solid electrolyte is more excellent.
Claims (10)
1. a preparation method for high efficiency zno-based dye-sensitized solar cell anode, is characterized in that: after configuring ZnO colloidal sol, utilizes described ZnO colloidal sol first making ZnO dense barrier layer in conductive substrates; Then chemical bath growth method is adopted, using six water nitrate and aqueous solution of urea as growth-promoting media, first carry out growth-promoting media preheating by sectional temperature control, then carry out the mode of growth response, described conductive substrates is prepared the zno-based nanometer sheet dye-sensitized solar cell anode film of Large-Area-Uniform densification.
2. the preparation method of high efficiency zno-based dye-sensitized solar cell anode according to claim 1, is characterized in that comprising the following steps:
(1) preparation of ZnO colloidal sol
Two water zinc acetates and monoethanolamine or diethanol amine are dissolved in making ZnO colloidal sol in EGME solution;
(2) preparation of ZnO dense barrier layer
Adopt stain leaching method, make conductive substrates apply ZnO colloidal sol; Then the conductive substrates scribbling ZnO colloidal sol is dried, calcined, thus obtain ZnO dense barrier layer in conductive substrates coating;
(3) preparation of the ZnO nano sheet film of vertical conduction substrate
(3-1) preparation of growth-promoting media
Using the mixed liquor of zinc nitrate hexahydrate and aqueous solution of urea as the growth-promoting media of chemical bath, described growth-promoting media is carried out be preheated to solution turned cloudy and start to occur crystallization;
(3-2) preparation of ZnO nano sheet film
By the described conductive substrates being coated with ZnO dense barrier layer, the growth-promoting media after putting into described preheating down with aufwuchsplate carries out growth response; Through rinsing, drying, calcine after reaction terminates, i.e. obtained zno-based nanometer sheet dye-sensitized solar cell anode.
3. the preparation method of high efficiency zno-based dye-sensitized solar cell anode according to claim 2, is characterized in that: in described step (3-1) after growth-promoting media preheating, adopt in ultrasonic process to solution and do not have bubble.
4. the preparation method of high efficiency zno-based dye-sensitized solar cell anode according to claim 2, is characterized in that: in described step (1), two water zinc acetates and monoethanolamine or the concentration of diethanol amine in EGME solution are respectively 0.20 ~ 0.60M.
5. the preparation method of high efficiency zno-based dye-sensitized solar cell anode according to claim 2, it is characterized in that: the bake out temperature scribbling the conductive substrates of ZnO colloidal sol in described step (2) is 60 ~ 120 DEG C, calcining heat is 250 ~ 500 DEG C, and temperature retention time is 30 ~ 120min.
6. the preparation method of high efficiency zno-based dye-sensitized solar cell anode according to claim 2, is characterized in that: the concentration of the zinc nitrate hexahydrate in described step (3-1) in growth-promoting media is 0.15 ~ 0.60M; The concentration of urea in growth-promoting media is 1.70 ~ 4.00M.
7. the preparation method of the high efficiency zno-based dye-sensitized solar cell anode according to Claims 2 or 3 or 6, is characterized in that: in described step (3-1), the preheat temperature of growth-promoting media is 60 ~ 90 DEG C, and warm-up time is 1 ~ 6h.
8. the preparation method of high efficiency zno-based dye-sensitized solar cell anode according to claim 2, is characterized in that: in described step (3-2), the temperature of growth response is 60 ~ 90 DEG C, and the reaction time is 2 ~ 6h.
9. the preparation method of high efficiency zno-based dye-sensitized solar cell anode according to claim 2, is characterized in that: in described step (3-2), bake out temperature is 60 ~ 120 DEG C; Calcining heat 250 ~ 450 DEG C.
10. the light anode utilizing the described preparation method of one of claim 1-9 to obtain, is characterized in that: described smooth anode is by ZnO dense barrier layer and have micropore and mesoporous ZnO nano sheet film forms; Described ZnO dense barrier layer is coated in conductive substrates; Described ZnO nano sheet standing upright is on ZnO dense barrier layer, and it is highly micron dimension, it is furnished with mesoporous; Interlaced, stacking and form micropore between described ZnO nano sheet.
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| CN105931849A (en) * | 2016-06-27 | 2016-09-07 | 景德镇陶瓷大学 | Preparation method of ZnO nanorod/nanosheet composite structure photo-anode film and photo-anode film prepared by preparation method |
| CN108155019A (en) * | 2017-12-22 | 2018-06-12 | 河南大学 | A kind of three-dimensional hierarchical structure ZnO film and its application in sensitization solar battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102693844A (en) * | 2012-05-30 | 2012-09-26 | 辽宁工业大学 | Method for preparing Al mixed with ZnO nanosheet array by adopting pulsed electromagnetic field |
| CN102983009A (en) * | 2012-11-06 | 2013-03-20 | 南京大学昆山创新研究院 | Flexible photo-anode of dye-sensitized solar cell based on zinc oxide nano-sheet and preparation of flexible photo-anode of dye-sensitized solar cell based on zinc oxide nano-sheet |
| CN104229867A (en) * | 2014-09-12 | 2014-12-24 | 中国科学院上海硅酸盐研究所 | Zinc oxide/strontium ruthenate core-shell nanowire and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102693844A (en) * | 2012-05-30 | 2012-09-26 | 辽宁工业大学 | Method for preparing Al mixed with ZnO nanosheet array by adopting pulsed electromagnetic field |
| CN102983009A (en) * | 2012-11-06 | 2013-03-20 | 南京大学昆山创新研究院 | Flexible photo-anode of dye-sensitized solar cell based on zinc oxide nano-sheet and preparation of flexible photo-anode of dye-sensitized solar cell based on zinc oxide nano-sheet |
| CN104229867A (en) * | 2014-09-12 | 2014-12-24 | 中国科学院上海硅酸盐研究所 | Zinc oxide/strontium ruthenate core-shell nanowire and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105931849A (en) * | 2016-06-27 | 2016-09-07 | 景德镇陶瓷大学 | Preparation method of ZnO nanorod/nanosheet composite structure photo-anode film and photo-anode film prepared by preparation method |
| CN108155019A (en) * | 2017-12-22 | 2018-06-12 | 河南大学 | A kind of three-dimensional hierarchical structure ZnO film and its application in sensitization solar battery |
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