CN108320911B - A kind of used by dye sensitization solar battery gel electrolyte and preparation method thereof - Google Patents
A kind of used by dye sensitization solar battery gel electrolyte and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of used by dye sensitization solar battery gel electrolytes, component including following parts by weight: 10-15 parts of tetracyanoethylene, 4-6 parts of 1- allyl -3- vinyl imidazole bromide, 1-3 parts of emulsifier, 0.05-0.1 parts of initiator, 1-2 parts of thermotropic liquid crystal polymer, 80-90 parts of hexa class ionic liquid, 2,4,6- tricyano -1,3,5- 3-7 parts of triazines, 5-10 parts of elemental iodine, 5-10 parts of additive.Used by dye sensitization solar battery gel electrolyte disclosed by the invention with conventional dyes sensitization solar battery electrolyte phase ratio disclosed in the prior art, conductivity is higher, stability is more preferable, it is easier to encapsulate, without organic solvent, safety is more preferable, and to proposing dye-sensitized solar cells incident photon-to-electron conversion efficiency and job stability is more effective.
Description
Technical field
The invention belongs to dye-sensitized solar cells technical fields, are related to a kind of dye-sensitized solar cells component,
Specifically, being related to a kind of used by dye sensitization solar battery gel electrolyte.
Background technique
In recent years, with the development of the global economy and people to environmental problem and energy problem understanding on go deep into, to clear
The demand of clean renewable energy device hastily increases.Dye-sensitized solar cells is exactly this kind of clean reproducible energy device
One of, since it has the advantages that high efficiency, low cost become focus of attention in the industry in recent years.
Electrolyte is one of critical component of dye-sensitized solar cells, is mainly risen in dye-sensitized solar cells
The effect of redox couple is transmitted, the superiority and inferiority of performance directly affects the photoelectric conversion efficiency of dye-sensitized solar cells and follows
Ring service life.Electrolyte for dye-sensitized solar cell mainly includes the following categories: liquid electrolyte, quasi-solid electrolyte
(gel electrolyte) and solid electrolyte；Traditional liquid electrolyte typically contain inorganic or organic iodide, iodine, additive with
And organic solvent etc., although it is with conductivity height, ion diffusion velocity is fast, the advantages that porous electrode good penetrability,
Organic solvent liquid electrolyte the disadvantages of there are volatile, encapsulation is difficult, stability is poor, toxicity is big and dyestuff easy desorption.Solid-state
Although electrolyte can effectively solve leakage, volatilization problems, but this kind of electrolytic conductivity is lower.
It is poly- that the Chinese invention patent of Patent No. 200610105327.0 discloses a kind of polymeric ionic liquid based gel
Polymer electrolyte and preparation method thereof, the electrolyte is by polymethacrylate polymeric ionic liquid, iodine, carbonic acid second
The mixture of enester and propene carbonate, polyacrylonitrile (PAN) and 0-0.5 parts of silica compositions.But this electrolyte contains
There are the conventional organic solvents such as ethylene carbonate and propene carbonate, is easy burning and leakage, and there is certain toxicity；Polypropylene
Nitrile only has the function of support carrier, and the migration of conductivity and iodine to gel electrolyte is not contributed.
Therefore, developing a kind of can effectively improve dye-sensitized solar cells stability and the dyestuff of photoelectric conversion efficiency is quick
It is imperative to change electrolyte used for solar batteries.
Summary of the invention
In order to overcome the defects of the prior art, the present invention provides a kind of used by dye sensitization solar battery gel electrolyte
Matter, the gel electrolyte raw material are easy to get, and preparation method is simple, not high to equipment requirement, cheap, are suitble to extensive raw
It produces；Compared with dye-sensitized solar cell electrolyte disclosed in the prior art, conductivity is higher, and stability is more preferable, is easier to
Encapsulation is free of organic solvent, and safety is more preferable, and to mentioning dye-sensitized solar cells incident photon-to-electron conversion efficiency and job stability
More effectively.
To achieve the above object of the invention, the technical solution adopted by the present invention is that, a kind of used by dye sensitization solar battery is solidifying
Glue electrolyte, the component including following parts by weight: 10-15 parts of tetracyanoethylene, 1- allyl -3- vinyl imidazole bromide 4-6
Part, 1-3 parts of emulsifier, 0.05-0.1 parts of initiator, 1-2 parts of thermotropic liquid crystal polymer, hexa class ionic liquid 80-
90 parts, 2,3-7 parts of 4,6- tricyanos -1,3,5-triazines, 5-10 parts of elemental iodine, 5-10 parts of additive.
Preferably, the additive is tolimidazole (MBI), butyl benzimidazole (NBB), tert .-butylpyridine
One or more of (TBP).
Preferably, the thermotropic liquid crystal polymer is selected from one or more of Xydar, Vectra, Rodrun.
Preferably, the emulsifier is selected from neopelex, polyoxypropylene polyethylene glycols ether, polyoxyethylene nonyl phenyl
One or more of vinethene.
Preferably, the initiator is selected from one or both of azodiisobutyronitrile, azobisisoheptonitrile.
Preferably, the preparation method of the hexa class ionic liquid, includes the following steps:
1) triethylamine is dissolved in organic solvent, after two alkane iodides are added thereto, be stirred to react 8- at 40-60 DEG C
10 hours, after washed 3-5 times with ether, solvent is evaporated off in back spin；
2) it will be added in tetrahydrofuran by the iodo quaternary amine that step 1) is prepared, and hexa-methylene is added thereto
Tetramine is stirred to react 6-8 hours at 50-60 DEG C, after washed 4-6 times with acetone, solvent is evaporated off in back spin.
Preferably, triethylamine described in step 1), organic solvent, two alkane iodides mass ratio be 1:(10-15): (2-
3)。
Preferably, the organic solvent is selected from one or more of ether, ethyl acetate, acetone.
Preferably, two alkane iodide is selected from-two iodobutane of Isosorbide-5-Nitrae, 1,3- diiodo propane, one in 1,5-, bis- iodopentane
Kind is several.
Preferably, iodo quaternary amine described in step 2), tetrahydrofuran, hexa mass ratio be (7-9):
(15-20): (1-2).
A kind of used by dye sensitization solar battery gel electrolyte and the dye sensitization using the gel electrolyte
The preparation method of solar battery includes the following steps: to mix each component according to the ratio of the parts by weight, ultrasonic 15-30
Minute, after it is injected into the battery case containing diaphragm material and positive and negative electrode complex by vacuum liquid filling equipment,
Battery case is heated at 60-80 DEG C and brings it about in-situ polymerization formation gel state, then gel is made by heating, vacuumize process
Electrolyte completely penetrates in diaphragm, after be packaged obtained gel electrolyte dye-sensitized solar cells.
The beneficial effects of adopting the technical scheme are that
1) used by dye sensitization solar battery gel electrolyte provided by the invention is in gel state, is had without containing volatile
Solvent effectively overcomes leakage problem, is conducive to improve dye-sensitized solar cells job stability.
2) used by dye sensitization solar battery gel electrolyte provided by the invention, raw material are easy to get, and preparation method is simply easy
Row, it is not high to equipment requirement, it is cheap, it is suitble to large-scale production.
3) used by dye sensitization solar battery gel electrolyte provided by the invention, it is quick with dyestuff disclosed in the prior art
Change solar cell electrolyte to compare, conductivity is higher, and stability is more preferable, is easier to encapsulate, and is free of organic solvent, safety is more
It is good, and to proposing dye-sensitized solar cells incident photon-to-electron conversion efficiency and job stability is more effective.
4) used by dye sensitization solar battery gel electrolyte provided by the invention is added to through in-situ polymerization synthesis
Ionomer, this quasi polymer not only have the function of supporting carrier, the migration of conductivity and iodine to gel electrolyte
It contributes, and the dye-sensitized solar cells incident photon-to-electron conversion efficiency using the gel electrolyte can be effectively improved, overcome
The lower technical problem of conventional solid-state electrolytic conductivity.
5) used by dye sensitization solar battery gel electrolyte provided by the invention adds 2,4,6- tricyano -1,3,5-
Triazine and thermotropic liquid crystal polymer are not only easy to encapsulate, and the migration of conductivity and iodine to gel electrolyte contributes, and energy
The dye-sensitized solar cells incident photon-to-electron conversion efficiency using the gel electrolyte is effectively improved, its stability can be also improved.
6) used by dye sensitization solar battery gel electrolyte provided by the invention adds hexa type ionic liquid
Body, this ionic liquid is in symmetrical mechanism, and ionic group ratio is more, can effectively improve the light of electrolytic conductivity and battery
Photoelectric transformation efficiency.
Specific embodiment
In order to make those skilled in the art more fully understand technical solution of the present invention, and make features described above of the invention,
Purpose and advantage are more clear understandable, and the present invention will be further explained with reference to the examples below.Embodiment is only used for
It is bright the present invention rather than limit the scope of the invention.
Present invention raw material as used in the following examples is from Sinopharm Chemical Reagent Co., Ltd..
Embodiment 1
A kind of used by dye sensitization solar battery gel electrolyte, the component including following parts by weight: tetracyanoethylene 10
Part, 4 parts of 1- allyl -3- vinyl imidazole bromide, 1 part of neopelex, 0.05 part of azodiisobutyronitrile, thermotropic liquid
1 part of crystalline polymer Xydar, 80 parts of hexa class ionic liquid, 3 parts of 2,4,6- tricyano -1,3,5- triazine, iodine list
5 parts of matter, 5 parts of tolimidazole (MBI).
The preparation method of the hexa class ionic liquid, includes the following steps:
1) triethylamine 10g is dissolved in ether 100g, after-two iodobutane 20g of Isosorbide-5-Nitrae is added thereto, stirred at 40 DEG C
Reaction 8 hours, after washed 3 times with ether, solvent is evaporated off in back spin；
2) it will be added in tetrahydrofuran 30g by the iodo quaternary amine 14g that step 1) is prepared, and six are added thereto
Methenamine 2g is stirred to react 6 hours at 50 DEG C, after washed 4 times with acetone, solvent is evaporated off in back spin.
A kind of used by dye sensitization solar battery gel electrolyte and the dye sensitization using the gel electrolyte
The preparation method of solar battery includes the following steps: to mix each component according to the ratio of the parts by weight, 15 points of ultrasound
Clock, after it is injected into the battery case containing diaphragm material and positive and negative electrode complex by vacuum liquid filling equipment, 60
Battery case is heated at DEG C and brings it about in-situ polymerization formation gel state, then gel electrolyte is made by heating, vacuumize process
Matter completely penetrates in diaphragm, after be packaged obtained gel electrolyte dye-sensitized solar cells.
Embodiment 2
A kind of used by dye sensitization solar battery gel electrolyte, the component including following parts by weight: tetracyanoethylene 12
Part, 5 parts of 1- allyl -3- vinyl imidazole bromide, 2 parts of polyoxypropylene polyethylene glycols ether, 0.07 part of azobisisoheptonitrile, heat
Cause 1 part of liquid crystal polymer Vectra, 83 parts of hexa class ionic liquid, 4 parts of 2,4,6- tricyano -1,3,5- triazine,
6 parts of elemental iodine, 6 parts of butyl benzimidazole (NBB).
The preparation method of the hexa class ionic liquid, includes the following steps:
1) triethylamine 10g is dissolved in ethyl acetate 120g, after 1,3- diiodo propane 22g is added thereto, at 45 DEG C
Be stirred to react 8.5 hours, after washed 4 times with ether, solvent is evaporated off in back spin；
2) it will be added in tetrahydrofuran 33g by the iodo quaternary amine 15g that step 1) is prepared, and six are added thereto
Methenamine 2.5g is stirred to react 6.5 hours at 53 DEG C, after washed 5 times with acetone, solvent is evaporated off in back spin.
A kind of used by dye sensitization solar battery gel electrolyte and the dye sensitization using the gel electrolyte
The preparation method of solar battery includes the following steps: to mix each component according to the ratio of the parts by weight, 20 points of ultrasound
Clock, after it is injected into the battery case containing diaphragm material and positive and negative electrode complex by vacuum liquid filling equipment, 65
Battery case is heated at DEG C and brings it about in-situ polymerization formation gel state, then gel electrolyte is made by heating, vacuumize process
Matter completely penetrates in diaphragm, after be packaged obtained gel electrolyte dye-sensitized solar cells.
Embodiment 3
A kind of used by dye sensitization solar battery gel electrolyte, the component including following parts by weight: tetracyanoethylene 13
Part, 5 parts of 1- allyl -3- vinyl imidazole bromide, 3 parts of nonylphenol polyoxyethylene ether, 0.08 part of azodiisobutyronitrile, thermotropic liquid
2 parts of crystalline polymer Rodrun, 86 parts of hexa class ionic liquid, 2,4,6- tricyano -1,3,5- triazin-6 part, iodine list
8 parts of matter, 8 parts of tert .-butylpyridine (TBP).
The preparation method of the hexa class ionic liquid, includes the following steps:
1) triethylamine 10g is dissolved in acetone 135g, after 1,5-, bis- iodopentane 25g is added thereto, stirred at 50 DEG C
Reaction 9 hours, after washed 5 times with ether, solvent is evaporated off in back spin；
2) it will be added in tetrahydrofuran 34g by the iodo quaternary amine 16g that step 1) is prepared, and six are added thereto
Methenamine 3g is stirred to react 7 hours at 56 DEG C, after washed 6 times with acetone, solvent is evaporated off in back spin.
A kind of used by dye sensitization solar battery gel electrolyte and the dye sensitization using the gel electrolyte
The preparation method of solar battery includes the following steps: to mix each component according to the ratio of the parts by weight, 20 points of ultrasound
Clock, after it is injected into the battery case containing diaphragm material and positive and negative electrode complex by vacuum liquid filling equipment, 72
Battery case is heated at DEG C and brings it about in-situ polymerization formation gel state, then gel electrolyte is made by heating, vacuumize process
Matter completely penetrates in diaphragm, after be packaged obtained gel electrolyte dye-sensitized solar cells.
Embodiment 4
A kind of used by dye sensitization solar battery gel electrolyte, the component including following parts by weight: tetracyanoethylene 14
Part, 6 parts of 1- allyl -3- vinyl imidazole bromide, 2 parts of emulsifier, 0.09 part of initiator, 1-2 parts of thermotropic liquid crystal polymer, six
88 parts of methenamine class ionic liquid, 2,5.5 parts of 4,6- tricyanos -1,3,5-triazines, 7 parts of elemental iodine, 8 parts of additive；Institute
The additive stated is tolimidazole (MBI), butyl benzimidazole (NBB), tert .-butylpyridine (TBP) 1:2:3 in mass ratio
Mixture forms；The thermotropic liquid crystal polymer is that Xydar, Vectra, Rodrun 2:3:5 mixture in mass ratio form；The cream
Agent is neopelex, polyoxypropylene polyethylene glycols ether, the nonylphenol polyoxyethylene ether mixture of 2:5:7 in mass ratio
It forms；The initiator is that azodiisobutyronitrile, azobisisoheptonitrile 3:8 mixture in mass ratio form.
The preparation method of the hexa class ionic liquid, includes the following steps:
1) triethylamine 10g is dissolved in ethyl acetate 140g, after 1,3- diiodo propane 28g is added thereto, at 57 DEG C
Be stirred to react 9.5 hours, after washed 5 times with ether, solvent is evaporated off in back spin；
2) it will be added in tetrahydrofuran 38g by the iodo quaternary amine 17g that step 1) is prepared, and six are added thereto
Methenamine 3.5g is stirred to react 7.5 hours at 58 DEG C, after washed 6 times with acetone, solvent is evaporated off in back spin.
A kind of used by dye sensitization solar battery gel electrolyte and the dye sensitization using the gel electrolyte
The preparation method of solar battery includes the following steps: to mix each component according to the ratio of the parts by weight, 27 points of ultrasound
Clock, after it is injected into the battery case containing diaphragm material and positive and negative electrode complex by vacuum liquid filling equipment, 77
Battery case is heated at DEG C and brings it about in-situ polymerization formation gel state, then gel electrolyte is made by heating, vacuumize process
Matter completely penetrates in diaphragm, after be packaged obtained gel electrolyte dye-sensitized solar cells.
Embodiment 5
A kind of used by dye sensitization solar battery gel electrolyte, the component including following parts by weight: tetracyanoethylene 15
Part, 6 parts of 1- allyl -3- vinyl imidazole bromide, 3 parts of polyoxypropylene polyethylene glycols ether, 0.1 part of azobisisoheptonitrile, heat
Cause 2 parts of liquid crystal polymer Vectra, 90 parts of hexa class ionic liquid, 7 parts of 2,4,6- tricyano -1,3,5- triazine,
10 parts of elemental iodine, 10 parts of tolimidazole (MBI).
The preparation method of the hexa class ionic liquid, includes the following steps:
1) triethylamine 10g is dissolved in ether 150g, after-two iodobutane 30g of Isosorbide-5-Nitrae is added thereto, stirred at 60 DEG C
Reaction 10 hours, after washed 5 times with ether, solvent is evaporated off in back spin；
2) it will be added in tetrahydrofuran 40g by the iodo quaternary amine 18g that step 1) is prepared, and six are added thereto
Methenamine 4g is stirred to react 8 hours at 60 DEG C, after washed 6 times with acetone, solvent is evaporated off in back spin.
A kind of used by dye sensitization solar battery gel electrolyte and the dye sensitization using the gel electrolyte
The preparation method of solar battery includes the following steps: to mix each component according to the ratio of the parts by weight, 30 points of ultrasound
Clock, after it is injected into the battery case containing diaphragm material and positive and negative electrode complex by vacuum liquid filling equipment, 80
Battery case is heated at DEG C and brings it about in-situ polymerization formation gel state, then gel electrolyte is made by heating, vacuumize process
Matter completely penetrates in diaphragm, after be packaged obtained gel electrolyte dye-sensitized solar cells.
Comparative example 1
This example provides a kind of gel electrolyte dye-sensitized solar cells, component with it is essentially identical in embodiment 1,
Unlike: 2,4,6- tricyano -1,3,5- triazine is not contained wherein.
Comparative example 2
This example provides a kind of gel electrolyte dye-sensitized solar cells, according to Chinese invention patent CN103489645B
Ten tripartite's method of embodiment is prepared.
By gel stain sensitization solar battery described in embodiment 1-5 and comparative example 1-2, at 25 DEG C, xenon lamp mould is used
Quasi- sunlight, light intensity 100mW/cm2Under the conditions of, measure battery (effective area 0.16cm2) photoelectric parameter is shown in Table 1.
1 dye-sensitized solar cells photoelectric properties parameter of table
As can be seen from the above table, gel electrolyte disclosed by the embodiments of the present invention is assembled into dye-sensitized solar cells
Afterwards, dye-sensitized solar cells photoelectric conversion efficiency is between 6.90-7.45%, and significantly larger than 1 photoelectric conversion of comparative example is imitated
Rate 6.56%, it is seen then that gel electrolyte disclosed by the embodiments of the present invention is conducive to improve the photoelectricity of dye-sensitized solar cells
The optical properties such as transformation efficiency, the addition of 2,4,6- tricyanos -1,3,5-triazines is to the light for improving dye-sensitized solar cells
Electrotransformation efficiency, open-circuit voltage and short circuit current have facilitation.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and what is described in the above embodiment and the description is only the present invention
Principle, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these variation and
Improvement is both fallen in the range of claimed invention.The present invention claims protection scope by appended claims and its
Equivalent defines.
Claims (9)
1. a kind of used by dye sensitization solar battery gel electrolyte, which is characterized in that the component including following parts by weight: four cyanogen
10-15 parts of base ethylene, 4-6 parts of 1- allyl -3- vinyl imidazole bromide, 1-3 parts of emulsifier, 0.05-0.1 parts of initiator, heat
Cause liquid crystal polymer 1-2 parts, 80-90 parts of hexa class ionic liquid, 3-7 parts of 2,4,6- tricyano -1,3,5- triazine,
5-10 parts of elemental iodine, 5-10 parts of additive；The additive is tolimidazole, butyl benzimidazole, tert .-butylpyridine
One or more of.
2. used by dye sensitization solar battery gel electrolyte according to claim 1, which is characterized in that the thermotropic liquid
Crystalline polymer is selected from one or more of Xydar, Vectra, Rodrun.
3. used by dye sensitization solar battery gel electrolyte according to claim 1, which is characterized in that the emulsifier
Selected from one or more of neopelex, polyoxypropylene polyethylene glycols ether, nonylphenol polyoxyethylene ether.
4. used by dye sensitization solar battery gel electrolyte according to claim 1, which is characterized in that the initiator
Selected from one or both of azodiisobutyronitrile, azobisisoheptonitrile.
5. used by dye sensitization solar battery gel electrolyte according to claim 1, which is characterized in that six methylene
The preparation method of urotropine class ionic liquid, includes the following steps:
1) triethylamine is dissolved in organic solvent, after two alkane iodides are added thereto, it is small to be stirred to react 8-10 at 40-60 DEG C
When, after washed 3-5 times with ether, solvent is evaporated off in back spin；
2) it will be added in tetrahydrofuran by the iodo quaternary amine that step 1) is prepared, and hexa-methylene four is added thereto
Amine is stirred to react 6-8 hours at 50-60 DEG C, after washed 4-6 times with acetone, solvent is evaporated off in back spin.
6. used by dye sensitization solar battery gel electrolyte according to claim 5, which is characterized in that institute in step 1)
State triethylamine, organic solvent, two alkane iodides mass ratio be 1:(10-15): (2-3).
7. used by dye sensitization solar battery gel electrolyte according to claim 5, which is characterized in that described organic molten
Agent is selected from one or more of ether, ethyl acetate, acetone；Two alkane iodide is selected from bis- iodobutane of 1,4-, 1,3- bis-
One or more of iodopropane, bis- iodopentane of 1,5-.
8. used by dye sensitization solar battery gel electrolyte according to claim 5, which is characterized in that institute in step 2)
State iodo quaternary amine, tetrahydrofuran, hexa mass ratio be (7-9): (15-20): (1-2).
9. a kind of using such as the battery of the described in any item used by dye sensitization solar battery gel electrolytes of claim 1-8
Preparation method, which comprises the steps of: mix each component according to the ratio of the parts by weight, ultrasonic 15-30 points
Clock, after it is injected into the battery case containing diaphragm material and positive and negative electrode complex by vacuum liquid filling equipment, in 60-
Battery case is heated at 80 DEG C and brings it about in-situ polymerization formation gel state, then makes gel electric by heating, vacuumize process
Solution matter completely penetrate in diaphragm, after be packaged obtained gel electrolyte dye-sensitized solar cells.
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