CN100411060C - Fused-salt type oligomer electrolyte and its use - Google Patents
Fused-salt type oligomer electrolyte and its use Download PDFInfo
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- CN100411060C CN100411060C CNB2005100115241A CN200510011524A CN100411060C CN 100411060 C CN100411060 C CN 100411060C CN B2005100115241 A CNB2005100115241 A CN B2005100115241A CN 200510011524 A CN200510011524 A CN 200510011524A CN 100411060 C CN100411060 C CN 100411060C
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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
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- Y02E10/542—Dye sensitized solar cells
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Abstract
The present invention belongs to the field of the manufacture technology of an electrolyte system in dye-sensitized solar cells, particularly to a fused salt type oligomer electrolyte composition and a preparation method thereof. The volumetric ratio of the fused salt type oligomer with low molecular weight in a fused salt type oligomer electrolyte and molten salt at the indoor temperature is from 1: 0 to 1: 3, the quantity of contained inorganic salt is from 0.3 to 3 M, and the mol ratio of an iodine simple-substance and I<-> contained in the fused salt type oligomer with low molecular weight, the molten salt at the indoor temperature and the inorganic salt is from 1: 20 to 1: 3. The fused salt type oligomer electrolyte is used for a dye-sensitized nanometer crystal film solar cell and can obtain the photoelectric conversion efficiency as high as 4.6 percent, and the electrolyte has difficult volatility; thereby, the problem that an original organic solvent electrolyte is easy to volatilize can be solved, and the present invention lays the foundation for the study of fused salt type polymer electrolytes.
Description
Technical field
The invention belongs to the manufacturing technology field of electrolyte system in the DSSC, particularly the fused-salt type oligomer electrolyte composition and use thereof.
Background technology
Along with the continuous growth of world population and the fast development of World Economics, the demand of the energy increases greatly.Most of so far energy all is these so-called fossil dyestuffs such as coal and oil, and these limited energy can be consumed totally eventually.Therefore seeking and develop the new energy is the most urgent task that the mankind face.And in all alternative energy sources, the development and use of solar energy have been caused people's extensive concern.Photovoltaic generation all has the important strategic meaning to changing the traditional energy structure and preserving the ecological environment.So development is low-cost, efficient, long-life solar-energy photo-voltaic cell is a key of utilizing solar power generation on a large scale.
Dye sensitization TiO
2Nano-crystal thin-film solar cell is a kind of novel photovoltaic power generation technology, and its operation principle and conventional silicon solar cell have very big difference.And this novel photovoltaic cell biggest advantage just is that preparation technology is simple, and is with low cost.Therefore development is low-cost, and high efficiency clear energy sources aspect has very big potentiality.
Traditional dye sensitization TiO
2The nano-crystal thin-film solar cell electrolyte mainly is made up of organic solvent and inorganic salt compounded of iodine and iodine.And this electrolytical shortcoming is that organic solvent is volatile, the long-time stability variation of the battery that causes.
In order to address the above problem, people have found out the whole bag of tricks and have substituted this traditional organic solvent electrolyte, as using p-N-type semiconductor N (people such as Kumara G R A, Nanocrystalline TiO
2Films fordye-sensitized solid-state solar cells.Key Engineering Materials, 2002,228～229:119～124), inorganic (people such as Bach U, Solid-state dye-sensitized mesoporous TiO
2Solarcells with high photon-to-electron conversion efficiencies, Nature, 1998,395:583～585; People such as Kr ü ger J, High efficiency solid-state photovoltaic device due toinhibition of interface charge recombination, Appl Phys Lett, 2085～2087) or organic (people such as Cao F, A solid-state 2001,79 (13):, dye sensitized photoelectrochemicalcell, J Phys Chem, 1995,99 (47): 17071～17073; People such as Matsumoto M, Adyesensitized TiO
2Photoelectrochemical cell constructed with polymer solidelectrolyte, Solid State Ionics, 1996,89:263～267) hole mobile material, polymer dielectric (people such as Kubo W, Quasi-solid state dye-sensitized TiO
2Solar cells:effectivecharge transport in mesoporous space filled with gel electrolytes containing iodideand iodine, J Phys chem.B, 2001,12809～12815), gel polymer electrolyte (people such as Ileperuma Q A 105 (51):, Dye-sensitised Photoelectrochemical solar cells withpolyacrylonitrile based solid polymer electrolytes, Electrochimica Acta, 2002,47:2801～2807; People such as Ren Y, A dye-sensitized nanoporpus TiO
2Photoelectrochemical cell with novel network polymer electrolyte, Journal ofApplied Electrochemistry, 2001,31:445～447; People such as Matsumoto M, Fabricationof solid-state dye-sensitized TiO
2Solar cell using polymer electrolyte, Bull ChemSoc Jpn, 2001,74 (2): 387～393) etc.But above-mentioned these methods are not to cause transformation efficiency low because the solid electrolyte conductivity is low, are exactly still to contain volatilizable micromolecule solvent in the electrolyte, and the problem of stability still can not get satisfied the solution.Therefore need seek to develop a kind of novel electrolytes, make it be applied to not only have in the DSSC higher transformation efficiency, and not volatile, and long-time stability are good.
People such as H.Ohno (Ionic conductivity of molten salts formed by polyether/salthybrids, Chemistry Letters, 1998,1:15; Molecular brush having molten saltdomain for fast ion conduction, Chemistry Letters, 1999,9:889; Molten salt typepolymer electrolytes, Electrochimica Acta, 2001,46:1407.) synthesized fused-salt type oligomer first, and discover that the chain end formation fused salt in poly(ethylene oxide) (PEO) can significantly improve conductivity, and point out that the fused-salt type polymer is to obtain the electrolytical brand-new developing direction of macroion conducting polymer.But they are not applied to this novel electrolyte in the battery.
All above-mentioned documents here are incorporated herein by reference in full.
Summary of the invention
An object of the present invention is to provide nonvolatile fused-salt type oligomer electrolyte composition, the DSSC that is assembled into this electrolyte composition has higher transformation efficiency, has also established the basis of practice simultaneously for the further research and development fused-salt type polymer dielectric of this fused-salt type oligomer electrolyte.
Another object of the present invention provides described fused-salt type oligomer electrolyte preparation of compositions method.
Also purpose of the present invention provides the purposes of described fused-salt type oligomer electrolyte composition.
The inventor is with fused-salt type oligomer, inorganic salts or combine with room temperature fused salt, obtained a kind of fused-salt type oligomer electrolyte composition nonvolatile and steady in a long-term, and with its first Application in dye sensitization nano-crystal thin-film solar cell, obtained higher ground electricity conversion surprisingly.
Fused-salt type oligomer electrolyte composition of the present invention contains at least a low-molecular-weight fused-salt type oligomer, one or more inorganic salts and elemental iodine, can further contain a kind of room temperature fused salt.
The low-molecular-weight fused-salt type oligomer in the described fused-salt type oligomer electrolyte and the volume ratio of room temperature fused salt are 1: 0～3, volume ratio is preferably 1: 1, the concentration of the iodide ion in the inorganic salts that contain is 0.3～3M, total mol ratio of contained I-is 1: 20～1: 3 in elemental iodine and room temperature fused salt and the inorganic salts, is preferably 1: 10～1: 5.
The structure of described room temperature fused salt is: B
+A
-
Wherein:
B
+: be selected from the glyoxaline cation of replacement, the structure of the glyoxaline cation of this replacement is as follows:
Wherein,
R
1It for carbon number 1～2 alkyl;
R
2It for carbon number 2～6 alkyl;
A
-: be selected from halide anion (Cl
-, Br
-Perhaps I
-); Trifluoromethyl sulfone anion; The mixture of one or more in two (trifluoromethyl sulfone) amine anion.
The inorganic salts that use in the fused-salt type oligomer electrolyte of the present invention are selected from a kind of in lithium iodide or the KI or their mixture etc.; Or be selected from more than one mixture in lithium iodide, lithium perchlorate, trifluoromethyl sulfonic acid lithium, the KI, and the concentration of iodide ion is 0.3～3M.
The fused-salt type oligomer that uses in the fused-salt type oligomer electrolyte of the present invention can be according to the known method preparation of those skilled in the art, for example document " Molecular brush having molten salt domainfor fast ion conduction " (people such as Ohno H, Chemistry letters, 1999 (9): the method for introducing 889-890), the document and the document of quoting in the document all are incorporated herein by reference with it in full at this.
This preparation method may further comprise the steps:
I) low-molecular-weight poly(ethylene oxide) is reacted with thionyl chloride in the presence of pyridine, generates the poly(ethylene oxide) of chloro;
The poly(ethylene oxide) of the chloro after ii) purifying again with the 1-methylimidazole at N, the N-dimethylformamide is 80 ℃ of 2 days 2 nights of reaction down, product is purified with absolute ether and is put in the vacuum drying oven dryly, obtaining a kind of anion is that chloride ion gets fused-salt type oligomer;
Iii) containing other anionic fused-salt type oligomers can obtain by ion-exchange.
The glyoxaline cation that the cation of described low-molecular-weight fused-salt type oligomer replaces for the low-molecular-weight poly(ethylene oxide), the structure of this glyoxaline cation is as follows:
Wherein, n is the repetition number of alkoxy chain on the substituting group, and preferably repeating number is 7～16; End group R can be H, OH, OCH
3Or polymerizable groups not such as Cl; Or end group R can be CH
2=CHCOO-, CH
2=CCH
3Polymerizable groups such as COO-.
The anion of described fused-salt type oligomer is selected from halide anion (Cl
-, Br
-Perhaps I
-), one or more the mixture in trifluoromethyl sulfone anion, two (trifluoromethyl sulfone) the amine anion.
The low-molecular-weight poly(ethylene oxide) of the synthesis material of the fused-salt type oligomer that uses in the fused-salt type oligomer electrolyte of the present invention is the commercially available prod, and its molecular weight is 150～750, preferred 350～750.
Fused-salt type oligomer electrolyte of the present invention can be used as electrolyte in the dye sensitization nano-crystal thin-film solar cell.
The application process of fused-salt type oligomer electrolyte composition of the present invention in the dye sensitization nano-crystal thin-film solar cell may further comprise the steps:
I) conventional method according to those skilled in the art prepares fused-salt type oligomer electrolyte composition of the present invention;
Ii) use conventional method well known by persons skilled in the art that above-mentioned oligomer electrolyte composition is assembled into dye sensitization nano-crystal thin-film solar cell, the work electrode of battery is for carrying the brilliant TiO that receives of dyestuff
2Membrane electrode is a platinized platinum to electrode;
Fused-salt type oligomer electrolyte used in the present invention, be used for dye sensitization nano-crystal thin-film solar cell and can obtain electricity conversion up to 4.6%, and this electrolyte has not effumability, solved the volatile problem of original organic solvent electrolyte and lays a good foundation for the research of fused-salt type polymer dielectric.
The present invention will further specify technical scheme of the present invention by following detailed.
Embodiment
Following detailed description refers to specific details of the present invention and special aspect, comprises particular embodiment of the present invention and example.And, for a better understanding of the present invention, will explain and define some specific terms.
Term used herein " fused-salt type oligomer electrolyte " refers to the electrolyte that contains fused-salt type oligomer, and oligomer is for polymer, and molecular weight is lower, and fused-salt type oligomer described here exists with the form of salt.
Term used herein " polyethylene oxide polymer (PEO) ", or claim " polyethylene glycol polymer (PEG) ", the polymer that refers to basically or mainly constitute by ethylene oxide unit.
The present invention can contain any required neccessary composition as described herein and optional member and/or qualifications, perhaps is made up of them, perhaps is made up of them basically.
Except as otherwise noted, all molecular weight all are weight average molecular weight.
Except as otherwise noted, all concentration all is molar concentration, and ratio all is mol ratio.
Except as otherwise noted, all mensuration is all at room temperature carried out, and also promptly carries out under about 25 ℃
The room temperature fused salt that uses in the fused-salt type oligomer electrolyte of the present invention can be according to the known any method preparation of those skilled in the art, for example document " ionic liquid progress " (people such as Li Yongfang, " chemistry circular ", 2002 (4): the method for introducing 243～250), the document and the document of quoting in the document all are incorporated herein by reference with it in full at this.
The present invention will be illustrated by following example, still, should be appreciated that the present invention is not limited to particular example as described herein and embodiment.The purpose that comprises these particular example and embodiment here is to help those of skill in the art to put into practice the present invention.Any those of skill in the art are easy to be further improved without departing from the spirit and scope of the present invention and perfect, therefore the present invention only is subjected to the restriction of the content and the scope of claim of the present invention, and its intention contains all and is included in alternative and equivalent in the spirit and scope of the invention that is limited by appendix claim.
Method of measurement
The dye sensitization nano-crystal thin-film solar cell uses the preparation of those skilled in the art's known method, for example, is not limited to, and uses at document " Conversion of light to electricity by cis-X
2Bis (2,2 '-bipyridyl-4,4 '-dicarboxylate) ruthenium (II) charge-transfer sensitizers (X=Cl
-, Br
-, I
-, CN
-, and SCN
-) on nanocrystalline TiO
2Electrodes " (
People such as M, J.Am.Chem.Soc., 1993,115 (14): the method for introducing 6382～6390) prepares needed dye sensitization nano-crystal TiO
2Work electrode and platinum plating be to electrode, and be assembled into battery and measure, and the document here is incorporated herein by reference in full with it.
(Model 273, EG﹠amp for potentiostat/galvanostat that the photoelectric properties of battery are computerizedd control; G) at room temperature measure.Light source uses the 250W tungsten halogen lamp, and incident intensity is 100mW/cm
2, illuminating area is 0.2cm
2Except as otherwise noted, the measurement of photoelectric properties of the present invention is all carried out under room temperature (25 ℃).
Embodiment 1
0.0015mol LiI (available from sigma company) is joined the low polyethylene glycol oxide (Mw=350) of 1--3-methylimidazole chlorine of 1mL, dissolve cooling fully to LiI 80 ℃ of heating 2 hours.And then to wherein adding 0.0005mol iodine (I
2), stirring and dissolving obtains by the battery of fused-salt type oligomer electrolyte of the present invention as the assembling of dye sensitization nano-crystal thin-film solar cell electrolyte, and the photoelectrochemical behaviour test result that records battery sees Table 1.
Embodiment 2
0.0015mol LiI is joined the low polyethylene glycol oxide (Mw=350) of 1--3-methylimidazole two (trifluoromethyl sulfone) amine of 1mL, dissolve cooling fully to LiI 80 ℃ of heating 2 hours.And then to wherein adding 0.0005mol iodine (I
2), stirring and dissolving obtains by the battery of fused-salt type oligomer electrolyte of the present invention as the assembling of dye sensitization nano-crystal thin-film solar cell electrolyte, and the photoelectrochemical behaviour test result that records battery sees Table 1.
Embodiment 3
0.0015mol LiI is joined the low polyethylene glycol oxide (Mw=350) of 1--3-methylimidazole iodine of 1mL, dissolve cooling fully to LiI 80 ℃ of heating 2 hours.And then to wherein adding 0.0005mol iodine (I
2), stirring and dissolving obtains by the battery of fused-salt type oligomer electrolyte of the present invention as the assembling of dye sensitization nano-crystal thin-film solar cell electrolyte, and the photoelectrochemical behaviour test result that records battery sees Table 1.
Embodiment 4
0.003mol LiI is joined the low polyethylene glycol oxide (Mw=750) of 1--3-methylimidazole chlorine of 1mL, dissolve cooling fully to LiI 80 ℃ of heating 3 hours.And then to wherein adding 0.0005 iodine (I
2), stirring and dissolving obtains by the battery of fused-salt type oligomer electrolyte of the present invention as the assembling of dye sensitization nano-crystal thin-film solar cell electrolyte, and the photoelectrochemical behaviour test result that records battery sees Table 1.
Embodiment 5
In the low polyethylene glycol oxide (Mw=350) of the 1--3-methylimidazole chlorine that 0.00075mol LiI is joined 0.5mL and the mixed solution of the 1-hexyl-3 methylimidazole iodine of 0.5mL, dissolve fully to LiI, cool off 80 ℃ of heating 2 hours.And then to wherein adding 0.0005 iodine (I
2), stirring and dissolving obtains by the battery of fused-salt type oligomer electrolyte of the present invention as the assembling of dye sensitization nano-crystal thin-film solar cell electrolyte, and the photoelectrochemical behaviour test result that records battery sees Table 1.
Embodiment 6
In the low polyethylene glycol oxide (Mw=350) of the 1--3-methylimidazole chlorine that 0.00075mol LiI is joined 0.5mL and the mixed solution of the 1-propyl group-3 methylimidazole iodine of 0.5mL, dissolve fully to LiI, cool off 80 ℃ of heating 2 hours.And then to wherein adding 0.0005mol iodine (I
2), stirring and dissolving obtains by the battery of fused-salt type oligomer electrolyte of the present invention as the assembling of dye sensitization nano-crystal thin-film solar cell electrolyte, and the photoelectrochemical behaviour test result that records battery sees Table 1.
Embodiment 7
In the low polyethylene glycol oxide (Mw=350) of the 1--3-methylimidazole chlorine that 0.00075mol LiI is joined 0.5mL and the mixed solution that the 1-butyl-the 3-methylimidazole is smelt of 0.5mL, dissolve fully to LiI, cool off 80 ℃ of heating 2 hours.And then to wherein adding 0.0005mol iodine (I
2), stirring and dissolving obtains by the battery of fused-salt type oligomer electrolyte of the present invention as the assembling of dye sensitization nano-crystal thin-film solar cell electrolyte, and the photoelectrochemical behaviour test result that records battery sees Table 1.
Embodiment 8
In the low polyethylene glycol oxide (Mw=350) of the 1--3-methylimidazole chlorine that 0.001125mol LiI is joined 0.75mL and the mixed solution of the 1-hexyl-3 methylimidazole iodine of 0.25mL, dissolve fully to LiI, cool off 80 ℃ of heating 2 hours.And then to wherein adding 0.0005mol iodine (I
2), stirring and dissolving obtains by the battery of fused-salt type oligomer electrolyte of the present invention as the assembling of dye sensitization nano-crystal thin-film solar cell electrolyte, and the photoelectrochemical behaviour test result that records battery sees Table 1.
Embodiment 9
In the low polyethylene glycol oxide (Mw=350) of the 1--3-methylimidazole chlorine that 0.000375mol LiI is joined 0.25mL and the mixed solution of the 1-hexyl-3 methylimidazole iodine of 0.75mL, dissolve fully to LiI, cool off 80 ℃ of heating 2 hours.And then to wherein adding 0.0005mol iodine (I
2), stirring and dissolving obtains by the battery of fused-salt type oligomer electrolyte of the present invention as the assembling of dye sensitization nano-crystal thin-film solar cell electrolyte, and the photoelectrochemical behaviour test result that records battery sees Table 1.
Embodiment 10
In the low polyethylene glycol oxide (Mw=350) of 1--3-methylimidazole two (trifluoromethyl sulfone) amine that 0.00075mol LiI is joined 0.5mL and the mixed solution of the 1-hexyl-3 methylimidazole iodine of 0.5mL, dissolve fully to LiI, cool off 80 ℃ of heating 2 hours.And then to wherein adding 0.0005mol iodine (I
2), stirring and dissolving obtains by the battery of fused-salt type oligomer electrolyte of the present invention as the assembling of dye sensitization nano-crystal thin-film solar cell electrolyte, and the photoelectrochemical behaviour test result that records battery sees Table 1.
Embodiment 11
In the low polyethylene glycol oxide (Mw=350) of the 1--3-methylimidazole iodine that 0.00075mol LiI is joined 0.5mL and the mixed solution of the 1-hexyl-3 methylimidazole iodine of 0.5mL, dissolve fully to LiI, cool off 80 ℃ of heating 2 hours.And then to wherein adding 0.0005mol iodine (I
2), stirring and dissolving obtains by the battery of fused-salt type oligomer electrolyte of the present invention as the assembling of dye sensitization nano-crystal thin-film solar cell electrolyte, and the photoelectrochemical behaviour test result that records battery sees Table 1.
Embodiment 12
In the low polyethylene glycol oxide (Mw=750) of the 1--3-methylimidazole chlorine that 0.0015mol LiI is joined 0.5mL and the mixed solution of the 1-hexyl-3 methylimidazole iodine of 0.5mL, dissolve fully to LiI, cool off 80 ℃ of heating 2 hours.And then to wherein adding 0.0005mol iodine (I
2), stirring and dissolving obtains by the battery of fused-salt type oligomer electrolyte of the present invention as the assembling of dye sensitization nano-crystal thin-film solar cell electrolyte, and the photoelectrochemical behaviour test result that records battery sees Table 1.
Embodiment 13
The low polyethylene glycol oxide (Mw=350) of 1--3-methylimidazole chlorine of 0.5mL is evenly mixed earlier with the 1-hexyl-3 methylimidazole iodine of 0.5mL, again to two (trifluoromethyl sulfone) amine lithiums that wherein add 0.000375mol successively and the LiI of 0.000375mol, dissolve cooling 80 ℃ of heating 2 hours fully to salt.And then to wherein adding 0.0005mol iodine (I
2), stirring and dissolving obtains by the battery of fused-salt type oligomer electrolyte of the present invention as the assembling of dye sensitization nano-crystal thin-film solar cell electrolyte, and the photoelectrochemical behaviour test result that records battery sees Table 1.
Embodiment 14
The low polyethylene glycol oxide (Mw=350) of 1--3-methylimidazole two (trifluoromethyl sulfone) amine of 0.5mL is evenly mixed earlier with the 1-hexyl-3 methylimidazole iodine of 0.5mL, again to two (trifluoromethyl sulfone) amine lithiums that wherein add 0.000375mol successively and the LiI of 0.000375mol, dissolve cooling 80 ℃ of heating 2 hours fully to salt.And then to wherein adding 0.0005mol iodine (I
2), stirring and dissolving obtains by the battery of fused-salt type oligomer electrolyte of the present invention as the assembling of dye sensitization nano-crystal thin-film solar cell electrolyte, and the photoelectrochemical behaviour test result that records battery sees Table 1.
Embodiment 15
The low polyethylene glycol oxide (Mw=350) of 1--3-methylimidazole chlorine of 0.5mL is evenly mixed earlier with the 1-hexyl-3 methylimidazole iodine of 0.5mL, again to wherein adding the lithium perchlorate of 0.000375mol and the LiI of 0.000375mol successively, dissolve cooling 80 ℃ of heating 2 hours fully to salt.And then to wherein adding 0.0005mol iodine (I
2), stirring and dissolving obtains by the battery of fused-salt type oligomer electrolyte of the present invention as the assembling of dye sensitization nano-crystal thin-film solar cell electrolyte, and the photoelectrochemical behaviour test result that records battery sees Table 1.
Embodiment 16
The low polyethylene glycol oxide (Mw=350) of 1--3-methylimidazole two (trifluoromethyl sulfone) amine of 0.5mL is evenly mixed earlier with the 1-hexyl-3 methylimidazole iodine of 0.5mL, again to wherein adding the lithium perchlorate of 0.000375mol and the LiI of 0.000375mol successively, dissolve cooling 80 ℃ of heating 2 hours fully to salt.And then to wherein adding 0.0005mol iodine (I
2), stirring and dissolving obtains by the battery of fused-salt type oligomer electrolyte of the present invention as the assembling of dye sensitization nano-crystal thin-film solar cell electrolyte, and the photoelectrochemical behaviour test result that records battery sees Table 1.
Embodiment 17
0.0015mol KI is joined the low polyethylene glycol oxide (Mw=350) of 1--3-methylimidazole chlorine of 1mL, dissolve cooling fully to KI 80 ℃ of heating 4 hours.And then to wherein adding 0.0005mol iodine (I
2), stirring and dissolving obtains by the battery of fused-salt type oligomer electrolyte of the present invention as the assembling of dye sensitization nano-crystal thin-film solar cell electrolyte, and the photoelectrochemical behaviour test result that records battery sees Table 1.
Embodiment 18
0.0015mol KI is joined the low polyethylene glycol oxide (Mw=350) of 1--3-methylimidazole two (trifluoromethyl sulfone) amine of 1mL, dissolve cooling fully to KI 80 ℃ of heating 4 hours.And then to wherein adding 0.0005mol iodine (I
2), stirring and dissolving obtains by the battery of fused-salt type oligomer electrolyte of the present invention as the assembling of dye sensitization nano-crystal thin-film solar cell electrolyte, and the photoelectrochemical behaviour test result that records battery sees Table 1.
Embodiment 19
0.0015mol LiI is joined low polyethylene glycol oxide (Mw=360)-3-methylimidazole two (trifluoromethyl sulfone) amine that the 1-acrylate of 1mL replaces, dissolve cooling fully to LiI 80 ℃ of heating 4 hours.And then to wherein adding 0.0005mol iodine (I
2), stirring and dissolving obtains by the battery of fused-salt type oligomer electrolyte of the present invention as the assembling of dye sensitization nano-crystal thin-film solar cell electrolyte, and the photoelectrochemical behaviour test result that records battery sees Table 1.
Table 1 photoelectric properties of the dye sensitization nano-crystal thin-film solar cell of fused-salt type oligomer electrolyte assembling of the present invention
| Embodiment | Short-circuit photocurrent mAcm -2 | Open circuit photovoltage V | Photoelectric conversion efficiency % |
| 1 | 5.75 | 0.68 | 2.88 |
| 2 | 6.85 | 0.60 | 3.00 |
| 3 | 1.35 | 0.60 | 0.51 |
| 4 | 6.70 | 0.64 | 3.14 |
| 5 | 7.35 | 0.63 | 3.13 |
| 6 | 4.40 | 0.69 | 2.13 |
| 7 | 2.45 | 0.70 | 1.25 |
| 8 | 6.05 | 0.62 | 2.41 |
| 9 | 7.05 | 0.58 | 2.22 |
| 10 | 11.35 | 0.63 | 4.60 |
| 11 | 5.45 | 0.61 | 2.16 |
| 12 | 12.60 | 0.68 | 6.12 |
| 13 | 6.35 | 0.59 | 2.21 |
| 14 | 7.90 | 0.62 | 3.34 |
| 15 | 6.55 | 0.60 | 2.27 |
| 16 | 8.60 | 0.62 | 3.80 |
| 17 | 2.75 | 0.56 | 0.98 |
| 18 | 6.00 | 0.58 | 2.45 |
| 19 | 2.25 | 0.54 | 0.91 |
Claims (7)
1. fused-salt type oligomer electrolyte, it is characterized in that: the low-molecular-weight fused-salt type oligomer in the described fused-salt type oligomer electrolyte and the volume ratio of room temperature fused salt are 1: 0～3, the concentration of the iodide ion in the inorganic salts that contain is 0.3～3M, contained I in elemental iodine and room temperature fused salt and the inorganic salts
-Total mol ratio be 1: 20～1: 3;
The glyoxaline cation that the cation of described low-molecular-weight fused-salt type oligomer replaces for the low-molecular-weight poly(ethylene oxide), the structure of this glyoxaline cation is:
Wherein, n is the repetition number of alkoxy chain on the substituting group, and repeating number is 7～16; End group R is H, OH, OCH
3Or Cl polymerizable groups not; Or end group R is CH
2=CHCOO-, CH
2=CCH
3The COO-polymerizable groups;
The anion of described low-molecular-weight fused-salt type oligomer is selected from Cl
-, Br
-, I
-, one or more the mixture in trifluoromethyl sulfone anion, two (trifluoromethyl sulfone) the amine anion;
The molecular weight of described low-molecular-weight poly(ethylene oxide) is 150～750.
2. fused-salt type oligomer electrolyte according to claim 1 is characterized in that: the volume ratio of described low-molecular-weight fused-salt type oligomer and room temperature fused salt is 1: 1.
3. fused-salt type oligomer electrolyte according to claim 1 is characterized in that: contained I in described elemental iodine and room temperature fused salt and the inorganic salts
-Total mol ratio be 1: 10～1: 5.
4. according to claim 1,2 or 3 described fused-salt type oligomer electrolytes, it is characterized in that: the structure of described room temperature fused salt is: B
+A
-
Wherein:
B
+: be selected from the glyoxaline cation of replacement, the structure of the glyoxaline cation of this replacement is:
Wherein,
R
1It for carbon number 1～2 alkyl;
R
2It for carbon number 2～6 alkyl;
A
-: be selected from Cl
-, Br
-, I
-, one or more the mixture in trifluoromethyl sulfone anion, two (trifluoromethyl sulfone) the amine anion.
5. according to claim 1 or 3 described fused-salt type oligomer electrolytes, it is characterized in that: described inorganic salts are selected from a kind of in lithium iodide or the KI or their mixture; Or be selected from more than one mixture in lithium iodide, lithium perchlorate, trifluoromethyl sulfonic acid lithium, the KI.
6. fused-salt type oligomer electrolyte according to claim 1 is characterized in that: the molecular weight of described low-molecular-weight poly(ethylene oxide) is 350～750.
7. purposes according to each described fused-salt type oligomer electrolyte of claim 1～6 is characterized in that: described fused-salt type oligomer electrolyte is as the electrolyte in the dye sensitization nano-crystal thin-film solar cell.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100115241A CN100411060C (en) | 2005-04-01 | 2005-04-01 | Fused-salt type oligomer electrolyte and its use |
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|---|---|---|---|
| CNB2005100115241A CN100411060C (en) | 2005-04-01 | 2005-04-01 | Fused-salt type oligomer electrolyte and its use |
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| Publication Number | Publication Date |
|---|---|
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| CN100411060C true CN100411060C (en) | 2008-08-13 |
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| CN1464002A (en) * | 2002-06-12 | 2003-12-31 | 中国科学院化学研究所 | Comb shaped polysiloxane and solid electrolyte produced therefrom and process for preparing the same |
| JP2004207451A (en) * | 2002-12-25 | 2004-07-22 | Sanyo Chem Ind Ltd | Electrolyte |
| JP2005044692A (en) * | 2003-07-24 | 2005-02-17 | Inst Of Research & Innovation | Electrolyte composition and photoelectrochemical cell using the composition |
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| CN1464002A (en) * | 2002-06-12 | 2003-12-31 | 中国科学院化学研究所 | Comb shaped polysiloxane and solid electrolyte produced therefrom and process for preparing the same |
| JP2004207451A (en) * | 2002-12-25 | 2004-07-22 | Sanyo Chem Ind Ltd | Electrolyte |
| JP2005044692A (en) * | 2003-07-24 | 2005-02-17 | Inst Of Research & Innovation | Electrolyte composition and photoelectrochemical cell using the composition |
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