CN110136964A - Flexibility for dye-sensitized solar cells is to electrode - Google Patents
Flexibility for dye-sensitized solar cells is to electrode Download PDFInfo
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- CN110136964A CN110136964A CN201910330904.3A CN201910330904A CN110136964A CN 110136964 A CN110136964 A CN 110136964A CN 201910330904 A CN201910330904 A CN 201910330904A CN 110136964 A CN110136964 A CN 110136964A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
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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
- Y02E10/542—Dye sensitized solar cells
Abstract
The present invention relates to a kind of flexibilities for dye-sensitized solar cells to electrode, and described includes trilaminate material to electrode, positioned at the polymeric layer of lower part, intermediate metal nano conductive layer and positioned at the carbon material layer on upper layer；The material for preparing of the carbon material layer includes various carbon materials and colloid, and the carbon material layer prepares material including at least carbon nanotube, four kinds of graphite, conductive black and graphene carbon materials.The present invention has the flexible conductive substrates layer of low-resistivity, high transparency, and the carbon material layer good film-forming property of coating, electric conductivity are excellent, catalytic activity is high.
Description
Technical field
The present invention relates to technical field of solar batteries, and in particular to a kind of flexibility for dye-sensitized solar cells is right
Electrode.
Background technique
Dye-sensitized solar cells (DSSC) mainly imitate photosynthesis principle, a kind of new type solar energy developed
Battery.DSSC is to simulate plant in nature using the nano-titanium dioxide of low cost and light-sensitive coloring agent as primary raw material and utilize too
Sun can be carried out photosynthesis, convert solar energy into electrical energy.DSSC due to its low in cost and preparation process simple feature by
To the close attention of scientific and technological circle, it is known as the third generation solar cell.DSSC is by light anode, electrolyte, form electrode.To electrode
It is the important component of DSSC, plays the role of going back original electrolyte.Platinum to electrode since its resistance is small and excellent catalytic effect,
It plates one layer of platinum mirror on electro-conductive glass to be used as to electrode, effect is fabulous.But the price of platinum is too high, is unfavorable for largely using, because
This finds that cheap, performance is good to electrode material, becomes as problem in the urgent need to address.Further, since flexible sun electricity
Pond has the characteristics that light weight, portable and bend resistance, can be used for solar telephone, solar sailor, in solar energy backpack etc., tool
There is biggish application potential, therefore flexible also extremely important to the preparation of electrode.
The carbon material conductive material good as a kind of stable chemical performance, thermal stability, for the reduction reaction of electrolyte
With preferable catalytic activity, and its price is far below noble metal platinum, thus is most potential in numerous substitution metal platinums
A kind of material.Carbon is based primarily upon graphite, active carbon, conductive black etc. to the research of electrode at present, by increasing its specific surface
It accumulates with conductivity and improves carbon to the catalytic activity of electrode, and then improve the transfer efficiency of battery.Although these carbon materials have
Good electro catalytic activity, and from a wealth of sources, it is cheap, but there are film formings that bad, blade coating is easy in conductive substrates
It falls off, easily occur to reunite, the problems such as industrialized production difficulty is big.
Summary of the invention
The present invention for the technical problems in the prior art, provides the flexibility for dye-sensitized solar cells to electricity
Pole can have the flexible conductive substrates layer of low-resistivity, high transparency, the carbon material layer good film-forming property of coating, electric conductivity
It is excellent, catalytic activity is high.
The technical scheme to solve the above technical problems is that a kind of flexibility for dye-sensitized solar cells is right
Electrode, described includes trilaminate material to electrode, positioned at the polymeric layer of lower part, intermediate metal nano conductive layer and is located at upper
The carbon material layer of layer；The material for preparing of the carbon material layer includes various carbon materials and colloid, and the carbon material layer prepares material
Material includes at least carbon nanotube, four kinds of graphite, conductive black and graphene carbon materials.
The beneficial effects of the present invention are: making electrode that there is low-resistivity, height to metal nano conductive layer is provided in electrode
The flexible conductive substrates layer of light transmittance；Using carbon material instead of platinum, stable chemical performance, thermal stability are good, for electricity
The reduction reaction for solving matter has preferable catalytic activity, and resistance to iodine corrodes, and cost greatly reduces；Carbon material layer is using a variety of
Carbon material and colloid are mixed, and form has good film forming or electric conductivity, catalytic activity compared with single carbon material, are conducive to improve
The photoelectric conversion efficiency of solar cell, and have it is preferable stretch and bending property, enabling manufactured has flexibility to electrode；
Of the invention is easily molded to electrode, Yi Shixian large area, industrialized production, easily regulates and controls to production preparation process.
Based on the above technical solution, the present invention can also be improved as follows.
Further, the material that the polymeric layer uses is polyethylene terephthalate (PET), poly- naphthalenedicarboxylic acid second
One of diol ester (PEN), polyimides (PI), polycarbonate (PC) and polyacrylate；It is preferred that using PET or polypropylene
Acid esters.
Beneficial effect using above-mentioned further scheme is: above-mentioned material is provided with certain translucency, and has good
Good high temperature resistance and mechanical performance can make have preferably flexible and optical property to electrode as substrate；And PET and
Polyacrylate performance is more excellent, and price is more cheap, can preferably reduce the cost to electrode.
Further, the metal nano conductive layer is metal nanowire thin-films；The gold that metal nanowire thin-films preferably use
Belonging to material is one or more of silver, copper, gold；Most preferably use silver nanowires film.
Beneficial effect using above-mentioned further scheme is: metal nano conductive layer is to change as conductive substrate layer
The electric conductivity of electrode can be effectively ensured whole using metal nanowire thin-films while guaranteeing electric conductivity for kind and raising
The mechanical performance and stability of a metal nano conductive layer, can have stable flexibility；And the selection of silver, copper, gold is then
It is the electric conductivity and stability in order to guarantee entire metal nanowire thin-films；Optimal use silver nanowires film is then sufficiently to examine
The electric conductivity and mechanical performance for having considered nano silver film are optimal.
Further, the colloid for preparing material of the carbon material layer is colloidal tio 2.
Beneficial effect using above-mentioned further scheme is: using colloidal tio 2, not only adhesiveness is good, and can also
The anti-uv-ray and catalytic activity of carbon material layer are effectively improved, it can be in the same of the film forming for greatling improve carbon material layer
When, improve the chemistry and optical stability of entire carbon material layer.
Further, the material for preparing of the carbon material layer further includes emulsifier.
Beneficial effect using above-mentioned further scheme is: emulsifier, which is added, can effectively improve point of colloidal tio 2
Dissipate property, enable carbon material layer carbon material and and titanium oxide colloid mixes more uniformly.
Further, four kinds of carbon nanotube in the carbon material layer, graphite, conductive black and graphene carbon materials according to 20~
The mixing of 40:8~16:2~4:5 mass ratio；The carbon nanotube, graphite, four kinds of carbon materials of conductive black and graphene it is excellent
Selecting mixed proportion is 20~30:10~15:3:5.
Beneficial effect using above-mentioned further scheme is: carbon nanotube have good orientation, certain translucency,
And flexible preferable, stable electrical properties when being bent after film forming；A small amount of conductive black is added can then improve carbon materials on the whole
The electric property of the bed of material；Meanwhile carbon nanotube has porous characteristic, specific surface area is higher, and a certain amount of graphite is added and then can
Enough catalytic activity for further improving carbon material layer；And graphene has good photosensitive property and electric property, is added one
The photosensitive property and electric property of carbon material layer can further be improved after quantitative graphite alkene, while can also be to entire carbon material
The film forming of layer has further raising；Using made of said ratio to application of electrode in dye-sensitized solar cells, can
Battery efficiency is set to stably reach 3.5% or more.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the embodiment of the present invention.
In attached drawing, parts list represented by the reference numerals are as follows:
1, polymeric layer, 2, metal nano conductive layer, 3, carbon material layer.
Specific embodiment
The principle and features of the present invention will be described below with reference to the accompanying drawings, and the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the invention.
As shown in Figure 1, a kind of flexibility for dye-sensitized solar cells that the present invention designs is to electrode, it include three layers
Material, positioned at the polymeric layer 1 of lower part, intermediate metal nano conductive layer 2 and positioned at the carbon material layer 3 on upper layer.Polymeric layer 1
As base material, metal nano conductive layer 2 is used as conductive substrate layer, and carbon material layer 3 plays conductive and catalysis dual effect
Fruit, and there is certain encapsulation performance.The material for preparing of the carbon material layer 3 includes various carbon materials and colloid, wherein extremely
It less include carbon nanotube, four kinds of graphite, conductive black and graphene carbon materials.Using multilayered structure and use various carbon materials
Mixing is the faultiness design based on current carbon material to electrode.Polymeric layer 1 can make entirely have flexibility of foundation to electrode,
And the electric property that the setting of carbon material layer 3 and metal nano conductive layer 2 then allows for simple carbon material is insufficient, increases metal
Conductive nano layer 2 can effectively improve the electric conductivity to electrode, while carbon material layer 3 can be used as encapsulating film, and metal is received
Rice conductive layer 2 and polymeric layer 1 are encapsulated into a flexible entirety well, and performance is stablized, be will not fall off.
It is to be based on that carbon material layer 3, which has selected at least four carbon materials to mix: carbon nanotube has good orientation,
Certain translucency, and flexible preferable, stable electrical properties when being bent after film forming；A small amount of conductive black is added then can be whole
The electric property of carbon material layer is improved on body；Meanwhile carbon nanotube has porous characteristic, specific surface area is higher, is added certain
The graphite of amount then can further improve the catalytic activity of carbon material layer；And graphene has good photosensitive property and electricity
Performance, the photosensitive property and electric property of carbon material layer can further be improved by being added after a certain amount of graphene, while can also
There is further raising to the film forming of entire carbon material layer.
The present invention also provides improved technical solutions, in improved technical solution, the material of the use of polymeric layer 1
Material is polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimides (PI), polycarbonate
(PC) and one of polyacrylate；It is preferred that using PET or polyacrylate.
The present invention also provides another improved technical solutions, and in improved technical solution, the metal nano is led
Electric layer 2 is metal nanowire thin-films；The metal material that metal nanowire thin-films preferably use is one of silver, copper, gold or several
Kind；Most preferably use silver nanowires film.
The present invention also provides another improved technical solutions, in improved technical solution, the carbon material layer 3
The colloid for preparing material is colloidal tio 2.The carbon material layer 3 prepares material emulsifier can also be added.
The present invention also provides another improved technical solutions, in improved technical solution, in the carbon material layer
Four kinds of carbon nanotube, graphite, conductive black and graphene carbon materials are mixed according to 20~40:8~16:2~4:5 mass ratio；
The carbon nanotube, graphite, four kinds of carbon materials of conductive black and graphene preferred mixed proportion be 20~30:10~15:3:
5。
Embodiment 1
S1, the pet substrate for choosing suitable size are cut into polymeric layer 1, cleaning, drying；
S2, the silver nanowires isopropanol that mass ratio is 2mg/ml is dispersed into solution with small-sized spray gun spraying in polymeric layer 1,
The metal nanometer line conductive layer 2 of silver-colored material has been plated on 1 surface of polymeric layer；
S3, carbon nanotube, graphite, conductive black and graphene four kinds of carbon materials 40:16:4:5 in mass ratio are mixed, is added
Enter colloidal tio 2 and emulsifier is fully ground；
S4, the slurry for obtaining S3 scratch on metal nanometer line conductive layer 2, become carbon material layer 3 after its drying, and
Flexibility is made to electrode.
By flexibility to electrode and light anode (structure: glass/FTO/TiO2/N719), iodine electrolyte (0.6 M1- propyl -3-
Methylpyridinium iodide imidazole salts, 0.5 M3- tert .-butylpyridine, 0.3 M LiI, 0.05 M I2 second eyeball solution) sandwich structure consisting
Dye-sensitized solar cells, measuring maximum photoelectric conversion efficiency is 4.6%.
Embodiment 2
S1, the PC substrate for choosing suitable size are cut into polymeric layer 1, cleaning, drying；
S2, polymeric layer 1 is put into magnetic control sputtering device, gold target is put into sputter, opened vacuum pump, work as vacuum degree
It is passed through protective atmosphere after reaching a certain level, controls discharge current by adjusting the intake of protective atmosphere, works as discharge current
Start sputter when reaching certain value, closes sputter after sputtering a period of time, plated golden material on 1 surface of polymeric layer
Metal nanometer line conductive layer 2；
S3, carbon nanotube, graphite, conductive black and graphene four kinds of carbon materials 20:12:3:5 in mass ratio are mixed, is added
Enter colloidal tio 2 and emulsifier is fully ground；
S4, the slurry for obtaining S3 scratch on metal nanometer line conductive layer 2, become carbon material layer 3 after its drying, and
Flexibility is made to electrode.
By flexibility to electrode and light anode (structure: glass/FTO/TiO2/N719), iodine electrolyte (0.6 M1- propyl -3-
Methylpyridinium iodide imidazole salts, 0.5 M3- tert .-butylpyridine, 0.3 M LiI, 0.05 M I2 second eyeball solution) sandwich structure consisting
Dye-sensitized solar cells, measuring maximum photoelectric conversion efficiency is 4.2%.
Embodiment 3
S1, the PEN substrate for choosing suitable size are cut into polymeric layer 1, cleaning, drying；
S2, the copper-bath for being 20mg/ml by mass ratio, are sprayed on polymeric layer 1, after air-drying, by polymeric layer 1
It is immersed in formalin, takes out after complete reaction, rinsed with clear water；It is then that mass ratio is different for the silver nanowires of 2mg/ml
Propyl alcohol disperses solution with small-sized spray gun spraying on the surface of copper nanometer layer, then has plated silver, composite copper material on 1 surface of polymeric layer
The metal nanometer line conductive layer 2 of matter；
S3, carbon nanotube, graphite, conductive black and graphene four kinds of carbon materials 30:8:2:5 in mass ratio are mixed, is added
Enter colloidal tio 2 and emulsifier is fully ground；
S4, the slurry for obtaining S3 scratch on metal nanometer line conductive layer 2, become carbon material layer 3 after its drying, and
Flexibility is made to electrode.
By flexibility to electrode and light anode (structure: glass/FTO/TiO2/N719), iodine electrolyte (0.6 M1- propyl -3-
Methylpyridinium iodide imidazole salts, 0.5 M3- tert .-butylpyridine, 0.3 M LiI, 0.05 M I2 second eyeball solution) sandwich structure consisting
Dye-sensitized solar cells, measuring maximum photoelectric conversion efficiency is 3.6%.
Embodiment 4
S1, glass substrate is cleaned by ultrasonic, is dry；
S2, the silver nanowires isopropanol dispersion solution of 2mg/ml is coated in the glass substrate of S1 with inker is scraped, is formed
The metal nanometer line conductive layer 2 of certain thickness silver material；
S3, the acrylic monomeric material that photoinitiator is added is coated in 2 surface of metal nanometer line conductive layer made from S2,
The time for irradiating 100 seconds or so in the UV lamp, the polymeric layer 1 of polyacrylate material is obtained, by polymeric layer 1 together with gold
Belong to nano wire conductive layer 2 to take off from glass substrate together；
S4, carbon nanotube, graphite, conductive black and graphene four kinds of carbon materials 30:10:3:5 in mass ratio are mixed, is added
Enter colloidal tio 2 and emulsifier is fully ground；
S5, the slurry for obtaining S4 scratch on metal nanometer line conductive layer 2, and carbon material layer 3 is made after its drying, and
Flexibility is made to electrode.
By flexibility to electrode and light anode (structure: glass/FTO/TiO2/N719), iodine electrolyte (0.6 M1- propyl -3-
Methylpyridinium iodide imidazole salts, 0.5 M3- tert .-butylpyridine, 0.3 M LiI, 0.05 M I2 second eyeball solution) sandwich structure consisting
Dye-sensitized solar cells, measuring maximum photoelectric conversion efficiency is 3.8%.
Embodiment 5
S1, the PI substrate for choosing suitable size are cut into polymeric layer 1, cleaning, drying；
S2, the copper-bath for being 20mg/ml by mass ratio, are sprayed on polymeric layer 1, after air-drying, by polymeric layer 1
It is immersed in formalin, takes out after complete reaction, rinsed with clear water, plated the gold of copper material on 1 surface of polymeric layer
Belong to nano wire conductive layer 2；
S3, carbon nanotube, graphite, conductive black and graphene four kinds of carbon materials 30:14:3:5 in mass ratio are mixed, is added
Enter colloidal tio 2 and emulsifier is fully ground；
S4, the slurry for obtaining S3 scratch on metal nanometer line conductive layer 2, become carbon material layer 3 after its drying, and
Flexibility is made to electrode.
By flexibility to electrode and light anode (structure: glass/FTO/TiO2/N719), iodine electrolyte (0.6 M1- propyl -3-
Methylpyridinium iodide imidazole salts, 0.5 M3- tert .-butylpyridine, 0.3 M LiI, 0.05 M I2 second eyeball solution) sandwich structure consisting
Dye-sensitized solar cells, measuring maximum photoelectric conversion efficiency is 4.1%.
Embodiment 6
S1, the PEN substrate for choosing suitable size are cut into polymeric layer 1, cleaning, drying；
S2, the silver nanowires isopropanol that mass ratio is 2mg/ml is dispersed into solution with small-sized spray gun spraying in polymeric layer 1,
The metal nanometer line conductive layer 2 of silver-colored material has been plated on 1 surface of polymeric layer；
S3, carbon nanotube, graphite, conductive black and graphene four kinds of carbon materials 30:12:4:5 in mass ratio are mixed, is added
Enter colloidal tio 2 and emulsifier is fully ground；
S4, the slurry for obtaining S3 scratch on metal nanometer line conductive layer 2, become carbon material layer 3 after its drying, and
Flexibility is made to electrode.
By flexibility to electrode and light anode (structure: glass/FTO/TiO2/N719), iodine electrolyte (0.6 M1- propyl -3-
Methylpyridinium iodide imidazole salts, 0.5 M3- tert .-butylpyridine, 0.3 M LiI, 0.05 M I2 second eyeball solution) sandwich structure consisting
Dye-sensitized solar cells, measuring maximum photoelectric conversion efficiency is 4.4%.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of flexibility for dye-sensitized solar cells is to electrode, it is characterised in that: described includes three layers of material to electrode
Material, positioned at the polymeric layer (1) of lower part, intermediate metal nano conductive layer (2) and positioned at the carbon material layer (3) on upper layer；It is described
The material for preparing of carbon material layer (3) includes various carbon materials and colloid, and the carbon material layer (3) prepares material including at least carbon
Four kinds of nanotube, graphite, conductive black and graphene carbon materials.
2. the flexibility according to claim 1 for dye-sensitized solar cells is to electrode, it is characterised in that: the polymerization
The material that nitride layer (1) uses is polyethylene terephthalate, polyethylene naphthalate, polyimides, polycarbonate
One of with polyacrylate.
3. the flexibility according to claim 2 for dye-sensitized solar cells is to electrode, it is characterised in that: the polymerization
The material that nitride layer (1) uses is polyethylene terephthalate or polyacrylate.
4. the flexibility according to claim 1 for dye-sensitized solar cells is to electrode, it is characterised in that: the metal
Conductive nano layer (2) is metal nanowire thin-films.
5. the flexibility according to claim 4 for dye-sensitized solar cells is to electrode, it is characterised in that: the metal
The metal material that the metal nanowire thin-films of conductive nano layer (2) use is one or more of silver, copper, gold.
6. the flexibility according to claim 5 for dye-sensitized solar cells is to electrode, it is characterised in that: the metal
The metal nanowire thin-films of conductive nano layer (2) are silver nanowires film.
7. the flexibility according to claim 1 for dye-sensitized solar cells is to electrode, it is characterised in that: the carbon materials
The colloid for preparing material of the bed of material (3) is colloidal tio 2.
8. the flexibility according to claim 5 for dye-sensitized solar cells is to electrode, it is characterised in that: the carbon materials
The material for preparing of the bed of material (3) further includes emulsifier.
9. the flexibility according to claim 1 for dye-sensitized solar cells is to electrode, it is characterised in that: the carbon materials
Four kinds of carbon nanotube, graphite, conductive black and graphene carbon materials are according to 20~40:8~16:2~4:5 matter in the bed of material (3)
Amount is than mixing.
10. the flexibility according to claim 7 for dye-sensitized solar cells is to electrode, it is characterised in that: the carbon
Four kinds of carbon nanotube, graphite, conductive black and graphene carbon materials are according to 20~30:10~15:3:5 matter in material layer (3)
Amount is than mixing.
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| CN201910330904.3A CN110136964A (en) | 2019-04-23 | 2019-04-23 | Flexibility for dye-sensitized solar cells is to electrode |
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| CN201910330904.3A CN110136964A (en) | 2019-04-23 | 2019-04-23 | Flexibility for dye-sensitized solar cells is to electrode |
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Citations (5)
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|---|---|---|---|---|
| CN103021509A (en) * | 2012-12-27 | 2013-04-03 | 中国科学院上海硅酸盐研究所 | Carbon size for dye sensitization solar cell counter electrode |
| CN104681283A (en) * | 2015-02-12 | 2015-06-03 | 宁波大学 | Modified carbon black and graphite counter electrode as well as preparation method and application thereof |
| CN105070510A (en) * | 2015-08-26 | 2015-11-18 | 长江大学 | Flexible dye-sensitized solar cell and preparation method thereof |
| CN204946727U (en) * | 2015-08-26 | 2016-01-06 | 长江大学 | Flexible dye-sensitized solar cell |
| CN105551834A (en) * | 2016-02-29 | 2016-05-04 | 长江大学 | Low-temperature and low-pressure preparation method of flexible dye-sensitized solar cell |
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2019
- 2019-04-23 CN CN201910330904.3A patent/CN110136964A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103021509A (en) * | 2012-12-27 | 2013-04-03 | 中国科学院上海硅酸盐研究所 | Carbon size for dye sensitization solar cell counter electrode |
| CN104681283A (en) * | 2015-02-12 | 2015-06-03 | 宁波大学 | Modified carbon black and graphite counter electrode as well as preparation method and application thereof |
| CN105070510A (en) * | 2015-08-26 | 2015-11-18 | 长江大学 | Flexible dye-sensitized solar cell and preparation method thereof |
| CN204946727U (en) * | 2015-08-26 | 2016-01-06 | 长江大学 | Flexible dye-sensitized solar cell |
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