CN108320912B - A kind of used by dye sensitization solar battery solid electrolyte based on ionic crystals - Google Patents
A kind of used by dye sensitization solar battery solid electrolyte based on ionic crystals Download PDFInfo
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- CN108320912B CN108320912B CN201810152492.4A CN201810152492A CN108320912B CN 108320912 B CN108320912 B CN 108320912B CN 201810152492 A CN201810152492 A CN 201810152492A CN 108320912 B CN108320912 B CN 108320912B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
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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
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
- H01G9/2009—Solid electrolytes
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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 invention discloses a kind of used by dye sensitization solar battery solid electrolyte based on ionic crystals, component including following parts by weight: 40-50 parts of cyanoimidazole type ionic crystals, (4- ferrocene acetenyl) is fullerene 3-7 parts aniline modified, and 5-10 parts of elemental iodine, 5-10 parts of additive.The additive is one or more of tolimidazole (MBI), butyl benzimidazole (NBB), tert .-butylpyridine (TBP).Used by dye sensitization solar battery solid electrolyte disclosed by the invention based on ionic crystals is compared with dye-sensitized solar cell electrolyte 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 more effective to raising dye-sensitized solar cells incident photon-to-electron conversion efficiency and job stability.
Description
Technical field
The invention belongs to technical field of solar batteries, are related to a kind of dye-sensitized solar cells component, specifically,
It is related to a kind of used by dye sensitization solar battery solid electrolyte based on ionic crystals.
Background technique
With the energy worsening shortages and environmental problem it is outstanding day by day, the exploitation of clean reproducible energy increasingly by
The concern of people also deepens continuously to the research of clean reproducible energy device solar battery.Dye-sensitized solar cells
As one of numerous solar batteries, paid close attention in the industry since it has the advantages that high efficiency, low cost become in recent years
Focus.
Electrolyte is the core component of dye-sensitized solar cells, mainly undertakes transmission redox couple, excites light
The superiority and inferiority of the effect of reducing dyes, performance directly affects solar battery efficiency and service life cycle.In the prior art often
The electrolyte for dye-sensitized solar cell seen has the diversified forms such as liquid, quasi- solid-state, solid-state.Wherein liquid electrolyte is general
Containing inorganic or organic iodide, iodine, additive and organic solvent etc., have conductivity high, ion diffusion velocity is fast, to more
The advantages that hole light anode good penetrability, but there is easy leakage, volatile, difficult encapsulation, high toxicity, stability difference and dyestuff legibility in it
The disadvantages of absorption；Due to containing a small amount of ethylene carbonate, propene carbonate, ionic liquid equal solvent in quasi-solid electrolyte,
The problem of there are still easy leakages, difficult encapsulation.Solid electrolyte has good long-time stability, but its conductivity is lower, leads
The dye-sensitized solar cells incident photon-to-electron conversion efficiency of solid electrolyte of applying preparation is lower.
Therefore, seek more efficient way, prepare while having the dye sensitization sun of high efficiency and high stability
Energy electrolyte for batteries has extensive market value and commercial applications prospect.
Summary of the invention
In order to overcome the defects of the prior art, the present invention provides a kind of dye sensitization of solar electricity based on ionic crystals
Pond solid electrolyte, which is easy to get, cheap；With dye sensitization of solar disclosed in the prior art
Cell electrolyte is compared, and conductivity is higher, and stability is more preferable, is easier to encapsulate, and is free of organic solvent, and safety is more preferable, and to mentioning
High dye-sensitized solar cells incident photon-to-electron conversion efficiency and job stability are more effective.
To achieve the above object of the invention, the technical solution adopted by the present invention is that, a kind of dye sensitization based on ionic crystals
Solid electrolyte used for solar batteries, the component including following parts by weight: 40-50 parts of cyanoimidazole type ionic crystals, (bis- cyclopentadienyl of 4-
Iron acetenyl) it is fullerene 3-7 parts aniline modified, 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 preparation method of the cyanoimidazole type ionic crystals, includes the following steps:
1) preparation of 1- alkyl -4,5- dicyano imidazole: 4,5- dicyano imidazole is dissolved in organic solvent, after thereto
Alkane iodide and basic catalyst is added, is stirred to react at 40-60 DEG C 8-10 hour, after by filtering, into reaction system
Water is added, liquid separation takes organic phase, and revolving removes organic solvent step, obtains 1- alkyl -4,5- dicyano imidazole；
2) preparation of cyanoimidazole type ionic crystals: the 1- alkyl -4,5- dicyano miaow that will be prepared by step 1)
Azoles is dissolved in ether, and addition and identical alkane iodide in step 1) thereto, is stirred to react at 40-50 DEG C 6-8 hours,
It is washed 5-7 times with ethyl acetate afterwards, revolving removes solvent.
Preferably, the quality of 4,5- dicyano imidazole described in step 1), organic solvent, alkane iodide, basic catalyst
Than for 1:(10-15): (1.5-2): (0.5-1).
Preferably, the organic solvent is selected from one or both of acetonitrile, chloroform；The basic catalyst is selected from hydrogen-oxygen
Change one or more of sodium, potassium hydroxide, sodium carbonate, potassium carbonate.
Preferably, the alkane iodide is selected from one or more of iodomethane, iodoethane, 1- iodopropane, 1- iodobutane.
Preferably, the dicyano imidazole of 1- alkyl -4,5- described in step 2), ether, alkane iodide mass ratio be (1.5-
2): (6-10): 1.
Preferably, the preparation method of described (4- ferrocene acetenyl) the aniline modified fullerene, includes the following steps:
1) it the preparation of epoxy-modified fullerene: disperses amino modified fullerene in fatty alcohol, and ring is added thereto
Oxygen chloropropane and potassium hydroxide flow back at 70-80 DEG C and are stirred to react 5-8 hours, and revolving removes solvent, use water centrifuge washing afterwards
It 5-7 times, is placed in baking in 100-110 DEG C of vacuum oven and obtains epoxy-modified fullerene；
2) it the preparation of (4- ferrocene acetenyl) aniline modified fullerene: will be prepared by step 1) epoxy-modified
Fullerene is scattered in high boiling solvent, then (4- ferrocene acetenyl) aniline is added thereto, is stirred to react at 70-80 DEG C
6-8 hours, revolving removed solvent, rear to use methylene chloride centrifuge washing 6-8 times, obtained (4- ferrocene acetenyl) aniline modified richness
Strangle alkene.
Preferably, the mass ratio of amino modified fullerene, fatty alcohol, epoxychloropropane, potassium hydroxide described in step 1)
For (3-5): (15-20): (1-2): 1.
Preferably, the fatty alcohol is selected from one or more of ethyl alcohol, isopropanol, n-butanol.
Preferably, the matter of epoxy-modified fullerene described in step 2), high boiling solvent, (4- ferrocene acetenyl) aniline
Amount is than being (3-6): (15-20): 1.
Preferably, the high boiling solvent is in dimethyl sulfoxide, N-Methyl pyrrolidone, n,N-Dimethylformamide
It is one or more of.
A kind of dye-sensitized solar cells, using the used by dye sensitization solar battery solid-state based on ionic crystals
Electrolyte is as electrolyte.
The beneficial effects of adopting the technical scheme are that
1) a kind of electrolyte for dye-sensitized solar cell based on ionic crystals provided by the invention is in solid-state, is free of
There is organic solvent, leakage problem is not present, is conducive to improve dye-sensitized solar cells job stability.
2) electrolyte for dye-sensitized solar cell provided by the invention based on ionic crystals, while being added to cyano
Imidazole type ionic crystals and (4- ferrocene acetenyl) aniline modified fullerene, the two synergistic effect, so that prepared electrolysis
Matter has excellent conductivity, and can effectively improve the dye-sensitized solar cells photoelectric conversion effect using the solid electrolyte
Rate overcomes the lower technical problem of conventional solid-state electrolytic conductivity.
3) electrolyte for dye-sensitized solar cell provided by the invention based on ionic crystals adds cyanoimidazole type
Ionic crystals, this ionic crystals are connected with cyano on imidazole ring, conjugated structure are constituted together with imidazole ring, are conducive to improve
Freeze thaw stability can also improve the performance of electrolyte, enhance the conductive capability and ionic mobility of electrolyte, and reason is
The ionic crystals is rich in electron group or strong electron-withdrawing group group, can be effectively acted in electrolyte by these functional groups
Ion (such as: with oxidation electricity to reacting) or working electrode is (such as: making TiO2Flat-band potential moves), in addition with to electrode
A little interactions occur for (enhancing its catalytic performance).
4) electrolyte for dye-sensitized solar cell provided by the invention based on ionic crystals is added to (bis- cyclopentadienyl of 4-
Iron acetenyl) aniline modified fullerene, ferrocene alkynyl, aniline and fullerene can enhance conductivity, with cyanoimidazole type from
Sub- crystal is applied in dye-sensitized solar cells together, can improve the open-circuit voltage and short circuit current of battery simultaneously, from
And largely improve the photoelectric conversion efficiency of battery.
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.
The present invention (4- ferrocene acetenyl) aniline as used in the following examples is that oneself is synthesized, and is synthesized referring to king
Lin Ping is studied, Hunan Normal University based on (4- ferrocene acetenyl) aniline/graphene complex electrochemical sensor.Its
His raw material is from upper Haiquan sunrise foreign trade Co., Ltd.
Embodiment 1
A kind of used by dye sensitization solar battery solid electrolyte based on ionic crystals, the group including following parts by weight
Point: 40 parts of cyanoimidazole type ionic crystals, aniline modified 3 parts of fullerene of (4- ferrocene acetenyl), and 5 parts of elemental iodine, methylbenzene
And 5 parts of imidazoles (MBI).
The preparation method of the cyanoimidazole type ionic crystals, includes the following steps:
1) preparation of 1- methyl -4,5- dicyano imidazole: 4,5- dicyano imidazole 10g is dissolved in acetonitrile 100g, backward
Wherein be added iodomethane 15g and sodium hydroxide 5g, be stirred to react at 40 DEG C 8 hours, after by filtering, into reaction system plus
Enter water, liquid separation takes organic phase, and revolving removes organic solvent step, obtains 1- methyl -4,5- dicyano imidazole；
2) preparation of cyanoimidazole type ionic crystals: the 1- methyl -4,5- dicyano miaow that will be prepared by step 1)
Azoles 15g is dissolved in ether 60g, and addition and iodomethane 10g in step 1) thereto, is stirred to react at 40 DEG C 6 hours, rear to use
Ethyl acetate washs 5 times, and revolving removes solvent.
The preparation method of (4- ferrocene acetenyl) the aniline modified fullerene, includes the following steps:
1) preparation of epoxy-modified fullerene: dispersing amino modified fullerene 30g in ethyl alcohol 150g, and adds thereto
Enter epoxychloropropane 10g and potassium hydroxide 10g, flow back and be stirred to react 5 hours at 70 DEG C, revolving remove solvent, afterwards with water from
The heart washs 5 times, is placed in baking in 100 DEG C of vacuum oven and obtains epoxy-modified fullerene；
2) it the preparation of (4- ferrocene acetenyl) aniline modified fullerene: will be prepared by step 1) epoxy-modified
Fullerene 30g is scattered in dimethyl sulfoxide 150g, then (4- ferrocene acetenyl) aniline 10g is added thereto, is stirred at 70 DEG C
Reaction 6 hours is mixed, revolving removes solvent, and it is rear to use methylene chloride centrifuge washing 6 times, it is aniline modified to obtain (4- ferrocene acetenyl)
Fullerene.
A kind of dye-sensitized solar cells, using the used by dye sensitization solar battery solid-state based on ionic crystals
Electrolyte is as electrolyte.
Embodiment 2
A kind of used by dye sensitization solar battery solid electrolyte based on ionic crystals, the group including following parts by weight
Point: 43 parts of cyanoimidazole type ionic crystals, aniline modified 4 parts of fullerene of (4- ferrocene acetenyl), and 7 parts of elemental iodine, butyl benzene
And 6 parts of imidazoles (NBB).
The preparation method of the cyanoimidazole type ionic crystals, includes the following steps:
1) preparation of 1- ethyl -4,5- dicyano imidazole: 4,5- dicyano imidazole 10g is dissolved in chloroform 120g, backward
Wherein be added iodoethane 17g and potassium hydroxide 6g, be stirred to react at 45 DEG C 8.5 hours, after by filtering, into reaction system
Water is added, liquid separation takes organic phase, and revolving removes organic solvent step, obtains 1- ethyl -4,5- dicyano imidazole；
2) preparation of cyanoimidazole type ionic crystals: the 1- ethyl -4,5- dicyano miaow that will be prepared by step 1)
Azoles 17g is dissolved in ether 78g, and addition and iodoethane 10g in step 1) thereto, is stirred to react at 43 DEG C 6.5 hours, after
It is washed 6 times with ethyl acetate, revolving removes solvent.
The preparation method of (4- ferrocene acetenyl) the aniline modified fullerene, includes the following steps:
1) it the preparation of epoxy-modified fullerene: disperses amino modified fullerene 35g in isopropanol 165g, and thereto
Be added epoxychloropropane 13g and potassium hydroxide 10g, flow back and is stirred to react 7 hours at 73 DEG C, revolving removing solvent, after use water
It centrifuge washing 6 times, is placed in baking in 104 DEG C of vacuum oven and obtains epoxy-modified fullerene；
2) it the preparation of (4- ferrocene acetenyl) aniline modified fullerene: will be prepared by step 1) epoxy-modified
Fullerene 40g is scattered in N-Methyl pyrrolidone 175g, then (4- ferrocene acetenyl) aniline 10g is added thereto, 75
It being stirred to react at DEG C 7 hours, revolving removes solvent, and it is rear to use methylene chloride centrifuge washing 7 times, obtain (4- ferrocene acetenyl) benzene
Amine modified fullerenes.
A kind of dye-sensitized solar cells, using the used by dye sensitization solar battery solid-state based on ionic crystals
Electrolyte is as electrolyte.
Embodiment 3
A kind of used by dye sensitization solar battery solid electrolyte based on ionic crystals, the group including following parts by weight
Point: 46 parts of cyanoimidazole type ionic crystals, aniline modified 5 parts of fullerene of (4- ferrocene acetenyl), and 7 parts of elemental iodine, tert-butyl
7 parts of pyridine (TBP).
The preparation method of the cyanoimidazole type ionic crystals, includes the following steps:
1) preparation of 1- propyl -4,5- dicyano imidazole: 4,5- dicyano imidazole 10g is dissolved in acetonitrile 135g, backward
Wherein be added 1- iodopropane 18g and sodium carbonate 7.5g, be stirred to react at 50 DEG C 9 hours, after by filtering, into reaction system
Water is added, liquid separation takes organic phase, and revolving removes organic solvent step, obtains 1- propyl -4,5- dicyano imidazole；
2) preparation of cyanoimidazole type ionic crystals: the 1- propyl -4,5- dicyano miaow that will be prepared by step 1)
Azoles 18g is dissolved in ether 80g, and thereto be added 1- iodopropane 10g, be stirred to react at 46 DEG C 7 hours, after use ethyl acetate
Washing 6 times, revolving remove solvent.
The preparation method of (4- ferrocene acetenyl) the aniline modified fullerene, includes the following steps:
1) it the preparation of epoxy-modified fullerene: disperses amino modified fullerene 40g in n-butanol 180g, and thereto
Be added epoxychloropropane 18g and potassium hydroxide 10g, flow back and is stirred to react 7 hours at 76 DEG C, revolving removing solvent, after use water
It centrifuge washing 7 times, is placed in baking in 106 DEG C of vacuum oven and obtains epoxy-modified fullerene；
2) it the preparation of (4- ferrocene acetenyl) aniline modified fullerene: will be prepared by step 1) epoxy-modified
Fullerene 50g is scattered in n,N-Dimethylformamide 185g, then (4- ferrocene acetenyl) aniline 10g is added thereto,
It being stirred to react at 77 DEG C 7 hours, revolving removes solvent, and it is rear to use methylene chloride centrifuge washing 7 times, obtain (4- ferrocene acetenyl)
Aniline modified fullerene.
A kind of dye-sensitized solar cells, using the used by dye sensitization solar battery solid-state based on ionic crystals
Electrolyte is as electrolyte.
Embodiment 4
A kind of used by dye sensitization solar battery solid electrolyte based on ionic crystals, the group including following parts by weight
Point: 48 parts of cyanoimidazole type ionic crystals, aniline modified 6 parts of fullerene of (4- ferrocene acetenyl), and 8 parts of elemental iodine, additive 8
Part；The additive be tolimidazole (MBI), butyl benzimidazole (NBB), tert .-butylpyridine (TBP) in mass ratio
2:3:5 mixture forms.
The preparation method of the cyanoimidazole type ionic crystals, includes the following steps:
1) preparation of 1- butyl -4,5- dicyano imidazole: 4,5- dicyano imidazole 10g is dissolved in chloroform 142g, backward
Wherein be added 1- iodobutane 19g and potassium carbonate 9g, be stirred to react at 55 DEG C 9.5 hours, after by filtering, into reaction system
Water is added, liquid separation takes organic phase, and revolving removes organic solvent step, obtains 1- butyl -4,5- dicyano imidazole；
2) preparation of cyanoimidazole type ionic crystals: the 1- butyl -4,5- dicyano miaow that will be prepared by step 1)
Azoles 19g is dissolved in ether 93g, and 1- iodobutane 10g is added thereto, is stirred to react at 48 DEG C 7.5 hours, uses acetic acid second afterwards
Ester washs 7 times, and revolving removes solvent.
The preparation method of (4- ferrocene acetenyl) the aniline modified fullerene, includes the following steps:
1) it the preparation of epoxy-modified fullerene: disperses amino modified fullerene 45g in fatty alcohol 190g, and thereto
Epoxychloropropane 18.5g and potassium hydroxide 10g is added, flows back and is stirred to react 7.5 hours at 78 DEG C, revolving removes solvent, after
With water centrifuge washing 6 times, it is placed in baking in 108 DEG C of vacuum oven and obtains epoxy-modified fullerene；The fatty alcohol is second
Alcohol, isopropanol, n-butanol 1:2:4 mixture in mass ratio form.
2) it the preparation of (4- ferrocene acetenyl) aniline modified fullerene: will be prepared by step 1) epoxy-modified
Fullerene 58g is scattered in N-Methyl pyrrolidone 190g, then (4- ferrocene acetenyl) aniline 10g is added thereto, 78
It being stirred to react at DEG C 7.5 hours, revolving removes solvent, and it is rear to use methylene chloride centrifuge washing 8 times, obtain (4- ferrocene acetenyl)
Aniline modified fullerene.
A kind of dye-sensitized solar cells, using the used by dye sensitization solar battery solid-state based on ionic crystals
Electrolyte is as electrolyte.
Embodiment 5
A kind of used by dye sensitization solar battery solid electrolyte based on ionic crystals, the group including following parts by weight
Point: 50 parts of cyanoimidazole type ionic crystals, aniline modified 7 parts of fullerene of (4- ferrocene acetenyl), and 10 parts of elemental iodine, butyl benzene
And 10 parts of imidazoles (NBB).
The preparation method of the cyanoimidazole type ionic crystals, includes the following steps:
1) preparation of 1- ethyl -4,5- dicyano imidazole: 4,5- dicyano imidazole 10g is dissolved in chloroform 150g, backward
Iodoethane 20g and basic catalyst 10g is wherein added, is stirred to react at 60 DEG C 10 hours, after by filtering, to reaction system
Middle addition water, liquid separation take organic phase, and revolving removes organic solvent step, obtains 1- ethyl -4,5- dicyano imidazole；The alkalinity
Catalyst is that sodium hydroxide, sodium carbonate 3:5 mixture in mass ratio form.
2) preparation of cyanoimidazole type ionic crystals: the 1- ethyl -4,5- dicyano miaow that will be prepared by step 1)
Azoles 20g is dissolved in ether 100g, and addition and identical iodoethane 10g in step 1) thereto, and it is small to be stirred to react 8 at 50 DEG C
When, after washed 7 times with ethyl acetate, revolving remove solvent.
The preparation method of (4- ferrocene acetenyl) the aniline modified fullerene, includes the following steps:
1) it the preparation of epoxy-modified fullerene: disperses amino modified fullerene 50g in isopropanol 200g, and thereto
Be added epoxychloropropane 20g and potassium hydroxide 10g, flow back and is stirred to react 8 hours at 80 DEG C, revolving removing solvent, after use water
It centrifuge washing 7 times, is placed in baking in 110 DEG C of vacuum oven and obtains epoxy-modified fullerene；
2) it the preparation of (4- ferrocene acetenyl) aniline modified fullerene: will be prepared by step 1) epoxy-modified
Fullerene 60g is scattered in n,N-Dimethylformamide 200g, then (4- ferrocene acetenyl) aniline 10g is added thereto,
It being stirred to react at 80 DEG C 8 hours, revolving removes solvent, and it is rear to use methylene chloride centrifuge washing 8 times, obtain (4- ferrocene acetenyl)
Aniline modified fullerene.
A kind of dye-sensitized solar cells, using the used by dye sensitization solar battery solid-state based on ionic crystals
Electrolyte is as electrolyte.
Comparative example 1
This example provides a kind of solid electrolyte, component with it is essentially identical in embodiment 1, unlike: be wherein free of
There is (4- ferrocene acetenyl) aniline modified fullerene.
Comparative example 2
This example provides a kind of solid electrolyte, is prepared into according to 13 method of Chinese invention patent CN102592832A embodiment
It arrives.
Quasi-solid electrolyte described in embodiment 1-5 and comparative example 1-2 is dripped into light anode dyestuff titanium dioxide film while hot
Between Pt electrode, further heating is filled out by vacuum so that gel electrolyte completely penetrates in titanium dioxide film perforated membrane
Technical form dye-sensitized solar cells is filled, at 25 DEG C, uses xenon lamp simulated solar irradiation, 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, solid electrolyte disclosed by the embodiments of the present invention is assembled into dye-sensitized solar cells
Afterwards, solar cell photoelectric transfer efficiency is between 6.52-7.22%, significantly larger than 1 incident photon-to-electron conversion efficiency 3.85% of comparative example,
As it can be seen that solid electrolyte disclosed by the embodiments of the present invention is conducive to improve the incident photon-to-electron conversion efficiency etc. of dye-sensitized solar cells
The addition of optical property, (4- ferrocene acetenyl) aniline modified fullerene turns the photoelectricity for improving dye-sensitized solar cells
Changing efficiency, open-circuit voltage and short circuit current has 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 solid electrolyte based on ionic crystals, which is characterized in that including weighing as follows
Measure the component of part: 40-50 parts of cyanoimidazole type ionic crystals, (4- ferrocene acetenyl) is fullerene 3-7 parts aniline modified, iodine list
5-10 parts of matter, 5-10 parts of additive；
Wherein, the preparation method of described (4- ferrocene acetenyl) the aniline modified fullerene, includes the following steps:
I) preparation of epoxy-modified fullerene: dispersing amino modified fullerene in fatty alcohol, and epoxy chlorine is added thereto
Propane and potassium hydroxide flow back at 70-80 DEG C and are stirred to react 5-8 hours, and revolving removes solvent, use water centrifuge washing 5-7 afterwards
It is secondary, it is placed in baking in 100-110 DEG C of vacuum oven and obtains epoxy-modified fullerene；
II) preparation of (4- ferrocene acetenyl) aniline modified fullerene: the epoxy-modified richness that will be prepared by step 1)
It strangles alkene to be scattered in high boiling solvent, then (4- ferrocene acetenyl) aniline is added thereto, be stirred to react 6- at 70-80 DEG C
8 hours, revolving removed solvent, rear to use methylene chloride centrifuge washing 6-8 times, obtained (4- ferrocene acetenyl) aniline modified fowler
Alkene.
2. the used by dye sensitization solar battery solid electrolyte according to claim 1 based on ionic crystals, feature
It is, the additive is one or more of tolimidazole, butyl benzimidazole, tert .-butylpyridine.
3. the used by dye sensitization solar battery solid electrolyte according to claim 1 based on ionic crystals, feature
It is, the preparation method of the cyanoimidazole type ionic crystals includes the following steps:
1) preparation of 1- alkyl -4,5- dicyano imidazole: 4,5- dicyano imidazole is dissolved in organic solvent, after be added thereto
Alkane iodide and basic catalyst are stirred to react 8-10 hours at 40-60 DEG C, after by filtering, be added into reaction system
Water, liquid separation take organic phase, and revolving removes organic solvent step, obtains 1- alkyl -4,5- dicyano imidazole；
2) preparation of cyanoimidazole type ionic crystals: the 1- alkyl -4,5- dicyano imidazole that will be prepared by step 1) is molten
In ether, and addition and identical alkane iodide in step 1) thereto, it is stirred to react at 40-50 DEG C 6-8 hours, it is rear to use
Ethyl acetate washs 5-7 times, and revolving removes solvent.
4. the used by dye sensitization solar battery solid electrolyte according to claim 3 based on ionic crystals, feature
Be, 4,5- dicyano imidazole described in step 1), organic solvent, alkane iodide, basic catalyst mass ratio be 1:(10-
15): (1.5-2): (0.5-1)；- the 4,5- of 1- alkyl described in step 2) dicyano imidazole, ether, alkane iodide mass ratio be
(1.5-2): (6-10): 1.
5. the used by dye sensitization solar battery solid electrolyte according to claim 3 based on ionic crystals, feature
It is, the organic solvent is selected from one or both of acetonitrile, chloroform；The basic catalyst is selected from sodium hydroxide, hydrogen-oxygen
Change one or more of potassium, sodium carbonate, potassium carbonate.
6. the used by dye sensitization solar battery solid electrolyte according to claim 3 based on ionic crystals, feature
It is, the alkane iodide is selected from one or more of iodomethane, iodoethane, 1- iodopropane, 1- iodobutane.
7. the used by dye sensitization solar battery solid electrolyte according to claim 1 based on ionic crystals, feature
Be, step I) described in amino modified fullerene, fatty alcohol, epoxychloropropane, potassium hydroxide mass ratio be (3-5):
(15-20): (1-2): 1；Epoxy-modified fullerene described in step 2), high boiling solvent, (4- ferrocene acetenyl) aniline
Mass ratio is (3-6): (15-20): 1.
8. the used by dye sensitization solar battery solid electrolyte according to claim 1 based on ionic crystals, feature
It is, the fatty alcohol is selected from one or more of ethyl alcohol, isopropanol, n-butanol；It is sub- that the high boiling solvent is selected from diformazan
One or more of sulfone, N-Methyl pyrrolidone, N,N-dimethylformamide.
9. a kind of solid using the used by dye sensitization solar battery according to claim 1-8 based on ionic crystals
Dye-sensitized solar cells of the state electrolyte as electrolyte.
Priority Applications (3)
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| CN201910273029.XA CN110010356B (en) | 2018-02-15 | 2018-02-15 | Preparation method of high-conductivity solid electrolyte |
| CN201810152492.4A CN108320912B (en) | 2018-02-15 | 2018-02-15 | A kind of used by dye sensitization solar battery solid electrolyte based on ionic crystals |
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| CN201810152492.4A Active CN108320912B (en) | 2018-02-15 | 2018-02-15 | A kind of used by dye sensitization solar battery solid electrolyte based on ionic crystals |
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| CN109545562B (en) * | 2018-12-01 | 2020-11-06 | 新沂市新南环保产业技术研究院有限公司 | Solid electrolyte for dye-sensitized solar cell |
| CN111261414B (en) * | 2020-02-13 | 2021-11-05 | 江苏日御光伏新材料科技有限公司 | Quasi-solid electrolyte for dye-sensitized solar cell and preparation method thereof |
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| KR100997843B1 (en) * | 2008-08-29 | 2010-12-01 | 주식회사 솔켐 | Dye-Sensitized Solar Cells Comprising Solid-State Electrolyte Containing Electrospun Polymer Nanofibers and The Preparing Method of The Same |
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| CN106653376A (en) * | 2016-12-30 | 2017-05-10 | 湖北工程学院 | Quasi solid electrolyte used for dye sensitized solar cell and preparation method thereof |
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| CN101436467A (en) * | 2008-12-15 | 2009-05-20 | 中国科学院长春应用化学研究所 | Ion liquid electrolyte containing bi-(fluorosulfonic acid) imines ion and iodine ion, and application thereof |
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| CN109988196A (en) | 2019-07-09 |
| CN108320912A (en) | 2018-07-24 |
| CN110010356A (en) | 2019-07-12 |
| CN110010356B (en) | 2021-06-29 |
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