CN1640931A - Volatileness-free polymer electrolyte composition, its preparation method and use - Google Patents
Volatileness-free polymer electrolyte composition, its preparation method and use Download PDFInfo
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- CN1640931A CN1640931A CN 200410002289 CN200410002289A CN1640931A CN 1640931 A CN1640931 A CN 1640931A CN 200410002289 CN200410002289 CN 200410002289 CN 200410002289 A CN200410002289 A CN 200410002289A CN 1640931 A CN1640931 A CN 1640931A
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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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- 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 electrolyte polymer composition without volatility and its preparation process. The electrolyte polymer composition contains at least one kind of ethylene oxide polymer; at least one kind of ionic liquid in the structure B+A-; at least one kind of organic or inorganic salt; at least one kind of optional stuffing; and proper amount of iodine. The preparation process includes mixing the said components at 50-150 deg.c. The electrolyte polymer composition without volatility may be used in, say, dye sensitized nanometer crystal film solar cell, and may result in unimaginable effect.
Description
Technical field
The present invention relates to a kind of non-volatility polymer electrolyte composition.
The invention still further relates to the preparation method of above-mentioned electrolyte composition.
The invention still further relates to the application of above-mentioned electrolyte composition.
Background technology
Energy dilemma and environmental pollution are the significant challenge that will face human future.Tapping a new source of energy with renewable and clean energy resource is one of five technical fields that have most 21 century the decision influence.Photovoltaic generation can be the side area people clean renewable energy source is provided, and has the important strategic meaning for preserving the ecological environment and changing the traditional energy structure.The main key of utilizing solar electrical energy generation on a large scale is to greatly develop low cost, efficient, long-life solar-energy photo-voltaic cell.
Dye sensitization TiO
2Nano-crystalline film photoelectric chemistry solar cell is a kind of novel photovoltaic power generation technology that grows up nineteen nineties, has the brand-new principle of design and the mechanism that are different from conventional solar cell.The particularly important is that this novel photovoltaic cell preparation technology is simple, material is cheap, aspect low-cost, low price, outstanding advantage is being arranged, very strong practical prospect is being arranged aspect, the high effect cleaning energy low-cost in development.
Dye sensitization TiO
2The liquid electrolyte that nano-crystalline film photoelectric chemistry solar cell generally adopts organic solvent and inorganic salt compounded of iodine and iodine to form.There is following problem in this electrolytic solution: 1. liquid electrolyte leaks easily, and organic solvent is volatile, and battery performance is descended, and working life shortens; 2. the solubleness of inorganic salt in organic solvent is limited, especially when battery is worked at low temperatures, generates precipitation easily; 3. organic solvent commonly used and cell sealing glue do not match.
In order to address the above problem, people have attempted several different methods and have substituted liquid electrolyte, as use room temperature fused salt (people such as Papageorgiou N, The performance and stability ofambient temperature molten salts for solar cell applications, J ElectrochemSoc, 3099～3108), p-N-type semiconductorN (people such as Kumara G R A, Nanocrystalline TiO 1996,143 (10):
2Films for dye-sensitized solid-state solar cells.KeyEngineering Materials, 2002,228-229:119～124), inorganic (people such as Bach U, Solid-state dye-sensitized mesoporous TiO
2Solar cells 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 to inhibition ofinterface 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, A dyesensitized 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:effective charge transport in mesoporous space filled with gel electrolytescontaining iodide and iodine, J Phys chem.B, 2001,12809～12815), gel polymer electrolyte (people such as Ileperuma Q A 105 (51):, Dye-sensitisedPhotoelectrochemical solar cells with polyacrylonitrile based solid polymerelectrolytes, Electrochimica Acta, 2002,47:2801～2807; People such as Ren Y, A dye-sensitized nanoporpus TiO
2Photoelectrochemical cell with novelnetwork polymer electrolyte, Journal of Applied Electrochemistry, 2001,31:445～447; People such as Matsumoto M, Fabrication of solid-state dye-sensitized TiO
2Solar cell using polymer electrolyte, Bull Chem Soc Jpn, 2001,387～393), in liquid electrolyte, add small molecules gelifying agent (people such as Kubo W 74 (2):, Quasi-solid-state dye-sensitized solar cells using room temperature molten salts and alow molecular weight gelator, Chem Commun, 2002, (4): 374～375) etc.But the efficiency of conversion of prepared battery is lower, or is still to contain the volatile small molecule solvent in the ionogen, and cell sealing and stability problem still need solve.Therefore need a kind of novel ionogen of exploitation, when it is assembled into dye-sensitized solar cells, have high conversion rate simultaneously, have good interface to contact with electrode and characteristic such as non-volatile, easy encapsulation.
People such as F.Croce (Nanocomposite polymer electrolytes for lithium batteries, Nature, 1998,394:456; Physical and chemical properties of nanocompositepolymer electrolytes, J.Phys.Chem.B, 1999,103:10632; Impedancespectroscopy study of PEO-based nanocomposite polymer electrolytes, J.Electrochem.Soc., 2000,147 (5): 1718) discover the inorganic compound of adding in polyethylene oxide (PEO), can improve ionic conductivity, reduce PEO degree of crystallinity, and at room temperature more stable with electrode interface.People such as G.Katsaros (A solvent-free compositepolymer/inorganic oxide electrolyte for high efficiency solid-state dye-sensitized solar cells, J.Photochem.Photobiol.A:Chem., 2002,149:191-198) will receive brilliant TiO
2Be compound in the polymer PEO polymer dielectric, be assembled into solid-state dye sensitized solar cell, increased the photoelectric transformation efficiency (η) of battery.But they do not use ionic liquid in this composite electrolyte, and the photoelectric transformation efficiency of conductivity and battery is still lower.
People (High efficiency dyed-sensitized nanocrystalline solarcells based on ionic liquid polymer gel electrolyte, Chem.Comm., 2002,2972-2973 such as M.Gr tzel; The performance and stability of ambient temperature molten saltsfor solar cell applications, J.Electrochem.Soc., 1996,143:3099; Gelation ofionic liquid-based electrolytes with silica nanoparticles for quasi-solid-statedye-sensitized solar cells, J.Am.Chem.Soc., 2003,125:1166) studies show that ionic liquid has high conductive capability, boiling point height, not volatile, advantages such as physics, chemical property are stablized, and electrochemical window is wide are with receiving brilliant SiO
2Solidify ionic liquid and be used for the dye sensitization nano-crystal thin-film solar cell, obtain comparatively ideal photoelectric properties.But they do not combine it with polymkeric substance, inorganic additives, and have added a small amount of volatile small molecule solvent, and efficiency of conversion is relatively low, and the leakage problem of battery does not still solve.
All above-mentioned documents here are incorporated herein by reference in full with it.
Summary of the invention
An object of the present invention is to provide the polymer electrolyte composition of non-volatility, the dye-sensitized solar cells that is assembled into this electrolyte composition has high conversion rate, simultaneously electrolyte composition contacts well with the interface of electrode, has characteristics such as non-volatile, easy encapsulation.
Another object of the present invention provides the method for the described polymer electrolyte composition of preparation.
A further object of the invention provides the application method of described polymer electrolyte composition.
Non-volatility polymer electrolyte composition provided by the invention, contain:
A) at least a or multiple polyethylene oxide polymer;
B) one or more an amount of ionic liquids, described ion liquid structure is: B
+A
-
Wherein, B
+Nonrestrictive comprising: imidazoles positively charged ion; The pyrazoles positively charged ion; The piperidines positively charged ion; The pyrrolidines positively charged ion; The pyroles positively charged ion; The indoles positively charged ion; The carbazoles positively charged ion; Quaternaries cation; Trialkyl sulfonium cationoid;
A
-Nonrestrictive comprising: halide anion (Cl
-, Br
-Perhaps I
-); The tetrafluoride boron anion; The phosphorus hexafluoride negatively charged ion; The antimonic fluoride negatively charged ion; Nitrate ion; Trifluoromethyl sulfone ion; Two (trifluoromethyl sulfone) amine negatively charged ion; Hydrofluoric acid root negatively charged ion (for example, H
2F
3 -Perhaps H
3F
4 -); Hexafluoro tantalum negatively charged ion; Hexafluoro niobium negatively charged ion;
C) randomly, the organic-or-inorganic salt that one or more are an amount of, nonrestrictive comprising: lithium salts, sodium salt, sylvite, quaternary ammonium salt; Condition is to work as components b) do not contain I
-The time, this organic or inorganic salt is salt compounded of iodine;
D) randomly, one or more an amount of mineral fillers;
E) an amount of iodine;
Condition is when amount of component b) when being not salt compounded of iodine, A
-Be I
-
The invention still further relates to the method for the described non-volatility polymer electrolyte composition of preparation, described method comprises uses ordinary method well known by persons skilled in the art that said components is mixed, and for example, but is not limited to stirring, grinding etc.
The invention still further relates to the application method of described non-volatility polymer electrolyte composition in the dye sensitization nano-crystal thin-film solar cell, described method comprises:
I) prepare non-volatility polymer electrolyte composition of the present invention according to the inventive method;
Ii) use ordinary method well known by persons skilled in the art that above-mentioned polymer electrolyte composition is assembled into the dye sensitization nano-crystal thin-film solar cell.
The present invention is combined with polyethylene oxide polymer, ionic liquid, inorganic additives etc., has obtained a kind of non-volatility polymer electrolyte composition, can satisfy the demand.
The present invention will obtain further instruction 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 " polymer " ionogen used herein ", refer to the ionogen that contains polymkeric substance, it generally also contains conductive organic-or-inorganic salt and small molecules softening agent.
Term used herein " ionic liquid ", or claim room temperature fused salt, refer to the liquid of forming by ion fully, be the salt that low temperature is in a liquid state, so-called here low temperature refers under＜100 ℃ temperature.
Term used herein " polyethylene oxide polymer (PEO) ", or title " polyethylene glycol polymer (PEG) ", the polymkeric substance that refers to basically or mainly be made of ethylene oxide unit, it can carry out modification by adding any required polymer unit, polymer segment etc.
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 percentage ratio and ratios all are weight ratio.
Except as otherwise noted, all mensuration is all at room temperature carried out, and also promptly carries out under about 25 ℃.
The present invention relates to the non-volatility polymer electrolyte composition, wherein said polymer electrolyte composition contains:
A) at least a or multiple polyethylene oxide polymer;
B) one or more an amount of ionic liquids, described ion liquid structure is: B
+A
-
Wherein,
B
+Nonrestrictive comprising: imidazoles positively charged ion; The pyrazoles positively charged ion; The piperidines positively charged ion; The pyrrolidines positively charged ion; The pyroles positively charged ion; The indoles positively charged ion; The carbazoles positively charged ion; Quaternaries cation; Trialkyl sulfonium cationoid;
A
-Nonrestrictive comprising: halide anion (Cl
-, Br
-Perhaps I
-); The tetrafluoride boron anion; The phosphorus hexafluoride negatively charged ion; The antimonic fluoride negatively charged ion; Nitrate ion; Trifluoromethyl sulfone ion; Two (trifluoromethyl sulfone) amine negatively charged ion; Hydrofluoric acid root negatively charged ion (for example, H
2F
3 -Perhaps H
3F
4 -); Hexafluoro tantalum negatively charged ion; Hexafluoro niobium negatively charged ion;
C) randomly, the organic-or-inorganic salt that one or more are an amount of, nonrestrictive comprising: lithium salts, sodium salt, sylvite, quaternary ammonium salt; Condition is to work as components b) do not contain I
-The time, this organic or inorganic salt is salt compounded of iodine;
D) randomly, one or more an amount of mineral fillers;
E) an amount of iodine;
Condition is when amount of component b) when being not salt compounded of iodine, A
-Be I
-
The polyethylene oxide polymer that uses in the non-volatility polymer dielectric of the present invention is commercially available or homemade polyethylene oxide polymer, and its molecular weight is 200-4,000,000, and preferred 350-4,000,000.
The ionic liquid that uses in the non-volatility polymer dielectric 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 ion liquid positively charged ion that uses in the non-volatility polymer dielectric of the present invention is preferably imidazoles positively charged ion and quaternaries cation, more preferably the imidazoles positively charged ion.
The cationic structure of using in the non-volatility polymer dielectric of the present invention of imidazoles is as follows:
Wherein,
R
1For carbonatoms is the alkyl of 1-2;
R
2For carbonatoms is the alkyl of 2-16, be preferably the alkyl that carbonatoms is 2-10, more preferably carbonatoms is the alkyl of 2-6.
The ion liquid negatively charged ion that uses in the non-volatility polymer dielectric of the present invention is preferably halide anion (Cl
-, Br
-Perhaps I
-); The tetrafluoride boron anion; Nitrate ion; Trifluoromethyl sulfone ion; Two (trifluoromethyl sulfone) amine negatively charged ion, more preferably I
-The tetrafluoride boron anion; Two (trifluoromethyl sulfone) amine negatively charged ion.
The more ion liquid examples that use in the non-volatility polymer dielectric of the present invention are, be not limited to 1-ethyl-3-Methylimidazole salt compounded of iodine, 1-propyl group-3-Methylimidazole salt compounded of iodine, 1-sec.-propyl-3-Methylimidazole salt compounded of iodine, 1-hexyl-3-Methylimidazole salt compounded of iodine, 1-butyl-3-Methylimidazole salt compounded of iodine, 1-hexadecyl-3-Methylimidazole salt compounded of iodine, 1-ethyl-3-Methylimidazole nitrate, 1-propyl group-3-Methylimidazole nitrate, 1-sec.-propyl-3-Methylimidazole nitrate, 1-hexyl-3-Methylimidazole nitrate, 1-butyl-3-Methylimidazole nitrate, 1-hexadecyl-3-Methylimidazole nitrate, 1-ethyl-3-Methylimidazole boron fluorate, 1-propyl group-3-Methylimidazole boron fluorate, 1-sec.-propyl-3-Methylimidazole boron fluorate, 1-hexyl-3-Methylimidazole boron fluorate, 1-butyl-3-Methylimidazole boron fluorate, 1-hexadecyl-3-Methylimidazole boron fluorate, 1-ethyl-3-Methylimidazole bromine salt, 1-propyl group-3-Methylimidazole bromine salt, 1-sec.-propyl-3-Methylimidazole bromine salt, 1-hexyl-3-Methylimidazole bromine salt, 1-butyl-3-Methylimidazole bromine salt, 1-hexadecyl-3-Methylimidazole bromine salt, 1-ethyl-3-Methylimidazole trifluoromethyl sulfonic acid, 1-propyl group-3-Methylimidazole trifluoromethyl sulfonic acid, 1-sec.-propyl-3-Methylimidazole trifluoromethyl sulfonic acid, 1-hexyl-3-Methylimidazole trifluoromethyl sulfonic acid, 1-butyl-3-Methylimidazole trifluoromethyl sulfonic acid, 1-hexadecyl-3-Methylimidazole trifluoromethyl sulfonic acid, 1-ethyl-3-Methylimidazole trifluoro sulfonic amine salt, 1-propyl group-3-Methylimidazole trifluoro sulfonic amine salt, 1-sec.-propyl-3-Methylimidazole trifluoro sulfonic amine salt, 1-hexyl-3-Methylimidazole trifluoro sulfonic amine salt, 1-butyl-3-Methylimidazole trifluoro sulfonic amine salt, 1-hexadecyl-3-Methylimidazole trifluoro sulfonic amine salt and their mixture.
The various ion liquid mechanism of action of using in the non-volatility polymer dielectric of the present invention is identical basically and is fully understood by those of skill in the art.Except having I
-Ionic liquid the I of providing also is provided
-Outside the part as redox couple, all ion liquid main effects all provide high electricity and lead and do not have a boiling characteristics.Any one those of skill in the art can derive other various ion liquid application easily from a kind of ion liquid application.Therefore, example of the present invention only is applied as the example explanation that makes an explanation with the part glyoxaline ion liquid.
The scope of the ion liquid consumption that uses in the non-volatility polymer dielectric of the present invention and the mass ratio of employed polyethylene oxide polymer is 1: 9-6: 1, be preferably 1: 4-4: 1, more preferably 1: 2-4: 1.
The organic-or-inorganic salt's who uses in the non-volatility polymer dielectric of the present invention example comprises, be not limited to, lithium iodide, lithium perchlorate, trifluoromethyl sulfonic acid lithium, sodium iodide, potassiumiodide, ammonium iodide, tetraethyl ammonium iodide, tetrapropyl ammonium iodide, tetrabutylammonium iodide etc., its consumption is 0-20%, based on the gross weight of polymer dielectric.
The organic-or-inorganic salt's who uses in the non-volatility polymer dielectric of the present invention mechanism of action is identical basically and is fully understood by those of skill in the art.Except having I
-The organic-or-inorganic salt I of providing also is provided
-Outside the part as redox couple, all organic-or-inorganic salts mainly act on and provide the part ion transport properties.Any one those of skill in the art can derive other various organic-or-inorganic salts' application easily from a kind of organic-or-inorganic salt's application.Therefore, example of the present invention only is applied as the example explanation that makes an explanation with the part organic-or-inorganic salt.
What use in the non-volatility polymer dielectric of the present invention is commercially available nanometer particle mineral filler, for example, is not limited to Nano titanium dioxide (for example, P25, Hombikat UV100 etc.), silicon-dioxide, gama-alumina, γ-LiAlO
2Deng.
The mechanism of action of the mineral filler of using in the non-volatility polymer dielectric of the present invention is identical basically and is fully understood by those of skill in the art.The main effect of all mineral fillers all is by suppressing the crystallization of polymkeric substance with polymkeric substance generation complexing action, leading thereby increase electrolytical electricity.Any one those of skill in the art can derive the application of other various mineral fillers easily from a kind of application of mineral filler.Therefore, example of the present invention only is applied as the example explanation that makes an explanation with Nano titanium dioxide.
The consumption of the mineral filler of using in the non-volatility polymer dielectric of the present invention is 1-20%, is preferably 5-10%, based on the gross weight of polymer dielectric.
The I that is contained among the consumption of employed iodine and components b and the c in the non-volatility polymer dielectric of the present invention
-Mol ratio be 1: 20-1: 2, be preferably 1: 10-1: 5.
The invention still further relates to the method for the described non-volatility polymer electrolyte composition of preparation, described method comprises uses ordinary method well known by persons skilled in the art that said components is mixed, for example, but be not limited to, stirring, grinding etc. are perhaps document " Composite PolymerElectrolytes " (people such as F.Croce, J.Electrochem.Soc., 1991,138 (7): the method for introducing 1918-1922), the document here is incorporated herein by reference in full with it.
In one embodiment of the invention, use the lower molecular weight polyethylene oxide polymer, under agitation condition other component is added successively after the heating for dissolving, the postcooling that stirs forms a kind of non-volatility polymer dielectric of the present invention.
In another embodiment of the invention, use the high molecular weight polyethylene oxide polymkeric substance, the preparation method is as follows: earlier a certain amount of mineral filler is under agitation joined in the anhydrous acetonitrile after molecular sieve is handled and be uniformly dispersed, add organic-or-inorganic salt, ionic liquid and iodine then respectively, mix, the last high molecular weight polyethylene oxide polymkeric substance that slowly adds, stirring is spent the night, after being uniformly dispersed, make solvent evaporates complete, obtain a kind of non-volatility polymer dielectric of the present invention.
The invention still further relates to the application method of described non-volatility polymer electrolyte composition in the dye sensitization nano-crystal thin-film solar cell, described method comprises:
I) prepare non-volatility polymer electrolyte composition of the present invention according to the inventive method, wherein said polymer electrolyte composition contains:
A) at least a or multiple polyethylene oxide polymer;
B) one or more an amount of ionic liquids, described ion liquid structure is: A
+B
-
Wherein,
B
+Nonrestrictive comprising: imidazoles positively charged ion; The pyrazoles positively charged ion; The piperidines positively charged ion; The pyrrolidines positively charged ion; The pyroles positively charged ion; The indoles positively charged ion; The carbazoles positively charged ion; Quaternaries cation; Trialkyl sulfonium cationoid;
A
-Nonrestrictive comprising: halide anion (Cl
-, Br
-Perhaps I
-); The tetrafluoride boron anion; The phosphorus hexafluoride negatively charged ion; The antimonic fluoride negatively charged ion; Nitrate ion; Trifluoromethyl sulfone ion; Two (trifluoromethyl sulfone) amine negatively charged ion; Hydrofluoric acid root negatively charged ion (for example, H
2F
3 -Perhaps H
3F
4 -); Hexafluoro tantalum negatively charged ion; Hexafluoro niobium negatively charged ion.Condition is when amount of component b) when being not salt compounded of iodine, A
-Be I
-
C) randomly, the organic-or-inorganic salt that one or more are an amount of, nonrestrictive comprising: lithium salts, sodium salt, sylvite, quaternary ammonium salt; Condition is to work as components b) do not contain I
-The time, this organic or inorganic salt is salt compounded of iodine;
D) randomly, one or more an amount of mineral fillers;
E) an amount of iodine;
Ii) use ordinary method well known by persons skilled in the art that above-mentioned polymer electrolyte composition is assembled into the dye sensitization nano-crystal thin-film solar cell.
Wherein, the definition of each component is as above in the described non-volatility polymer electrolyte composition of the present invention.
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 alternatives and equivalent in the spirit and scope of the invention that is limited by appendix claim.
Measuring method
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 bycis-X
2Bis (2,2 '-bipyridyl-4,4 '-dicarboxylate) ruthenium (II) charge-transfersensitizers (X=Cl
-, Br
-, I
-, CN
-, and SCN
-) on nanocrystalline TiO
2Electrodes " (1993,115 (14): the method for introducing 6382～6390) prepares needed dye sensitization nano-crystal TiO for people such as Gr tzel M, J.Am.Chem.Soc.
2Working electrode and platinum plating counter electrode, and be assembled into battery and measure, 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 halogen tungsten 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
Control 1-propyl group 3-Methylimidazole salt compounded of iodine and PEO (Mw=4,000,000, at 50 ℃ of vacuum-drying 24h) amount ratio be 1: 9, the content of LiI in the ionogen (available from Sigma company, vacuum-drying 24h under 200 ℃ of conditions) is 10 weight %, nano titanium oxide (P25, available from Degussa company, vacuum-drying 24h under 250 ℃ of conditions) content is 6 weight %, iodine and I
-Mol ratio be 1: 10.
Preparation process is as follows: nano titanium oxide is under agitation joined in an amount of acetonitrile (dewatering through the molecular sieve processing), add LiI and I then respectively
2, 1-propyl group 3-Methylimidazole salt compounded of iodine, the last PEO that slowly adds, stirring is spent the night, and after being uniformly dispersed, at room temperature makes solvent evaporates to muddy.Down above-mentioned ionogen is coated in prepared dye sensitization nano porous polycrystalline TiO at 70 ℃ then
2The membrane electrode surface after the equal solvent volatilization fully, above the platinum plating counter electrode is overlying on, clamps, and is cooled to room temperature, obtains the solid state battery by non-volatility polymer dielectric preparation of the present invention.The photoelectrochemical behaviour test result of battery sees Table I.
Embodiment 2
Except the amount ratio of 1-propyl group 3-Methylimidazole salt compounded of iodine and PEO becomes 1.2: 1, the assemble method of other components contents, electrolyte preparation method and dye-sensitized solar cells is all identical with embodiment 1, and the photoelectrochemical behaviour test result of battery sees Table I.
Embodiment 3
Except the amount ratio of 1-propyl group 3-Methylimidazole salt compounded of iodine and PEO becomes 6: 1, the assemble method of other components contents, electrolyte preparation method and dye-sensitized solar cells is all identical with embodiment 1, and the photoelectrochemical behaviour test result of battery sees Table I.
Embodiment 4
Except TiO
2Content become outside 0%, the assemble method of other components contents, electrolyte preparation method and dye-sensitized solar cells is all identical with embodiment 2, the photoelectrochemical behaviour test result of battery sees Table I.
Embodiment 5
Except TiO
2Content become outside 20%, the assemble method of other components contents, electrolyte preparation method and dye-sensitized solar cells is all identical with embodiment 2, the photoelectrochemical behaviour test result of battery sees Table I.
Embodiment 6
Except iodine and I
-Mol ratio become outside 1: 20, the assemble method of other components contents, electrolyte preparation method and dye-sensitized solar cells is all identical with embodiment 2, the photoelectrochemical behaviour test result of battery sees Table I.
Embodiment 7
Except iodine and I
-Mol ratio become outside 1: 2, the assemble method of other components contents, electrolyte preparation method and dye-sensitized solar cells is all identical with embodiment 2, the photoelectrochemical behaviour test result of battery sees Table I.
Embodiment 8
Except the content of LiI becomes 20%, the assemble method of other components contents, electrolyte preparation method and dye-sensitized solar cells is all identical with embodiment 2, and the photoelectrochemical behaviour test result of battery sees Table I.
The comparative example 1
Except not containing the ionic liquid, the assemble method of other components contents, electrolyte preparation method and dye-sensitized solar cells is all identical with embodiment 2, and the photoelectrochemical behaviour test result of battery sees Table I.
Embodiment 9
The amount ratio of control 1-hexyl 3-Methylimidazole salt compounded of iodine and poly glycol monomethyl ether (Mw=750 is available from Aldrich company) is 1: 1, and the content of LiI is 10 weight % in the ionogen, iodine and I
-Mol ratio be 1: 10.
The preparation method is as follows: 1-hexyl-3-Methylimidazole salt compounded of iodine, LiI and iodine are joined in the 25ml round-bottomed flask that the poly glycol monomethyl ether after the vacuum-drying is housed, stirred 1 hour down at 60 ℃ then, make it to mix fully, obtain a kind of non-volatility polymer dielectric of the present invention.This polymer dielectric is assembled into dye-sensitized solar cells measures, the photoelectrochemical behaviour test result of battery is listed Table I in.
Embodiment 10
Except LiI being become 1-ethyl-3-Methylimidazole fluoroborate, the assemble method of the content of all components, electrolyte preparation method and dye-sensitized solar cells is all identical with embodiment 9, and the photoelectrochemical behaviour test result of battery sees Table I.
Embodiment 11
Except LiI being become 1-ethyl-3-Methylimidazole bromine salt, the assemble method of the content of all components, electrolyte preparation method and dye-sensitized solar cells is all identical with embodiment 9, and the photoelectrochemical behaviour test result of battery sees Table I.
Embodiment 12
Except LiI is become the trifluoromethyl sulfonic acid lithium, the assemble method of the content of all components, electrolyte preparation method and dye-sensitized solar cells is all identical with embodiment 9, and the photoelectrochemical behaviour test result of battery sees Table I.
Embodiment 13
Except not containing the LiI, the assemble method of the content of all components, electrolyte preparation method and dye-sensitized solar cells is all identical with embodiment 9, and the photoelectrochemical behaviour test result of battery sees Table I.
Embodiment 14
Except 1-hexyl 3-Methylimidazole salt compounded of iodine is become 1-ethyl-3-Methylimidazole salt compounded of iodine, the assemble method of the content of all components, electrolyte preparation method and dye-sensitized solar cells is all identical with embodiment 13, and the photoelectrochemical behaviour test result of battery sees Table I.
Embodiment 15
Except 1-ethyl 3-Methylimidazole salt compounded of iodine and poly glycol monomethyl ether (Mw=750, available from Aldrich company) amount ratio become outside 1: 2, the assemble method of other components contents, electrolyte preparation method and dye-sensitized solar cells is all identical with embodiment 14, and the photoelectrochemical behaviour test result of battery sees Table I.
Embodiment 16
Except iodine and I
-Mol ratio become outside 1: 5, the assemble method of other components contents, electrolyte preparation method and dye-sensitized solar cells is all identical with embodiment 15, the photoelectrochemical behaviour test result of battery sees Table I.
The Table I photoelectric properties of the dye sensitization nano-crystal thin-film solar cell of non-volatility polymer dielectric assembling of the present invention
| Embodiment | Short-circuit photocurrent (mA cm -2) | Photoelectric transformation efficiency (%) |
| ???1 | ?4.1 | ????1.12 |
| ???2 | ?6.2 | ????2.50 |
| ???3 | ?5.8 | ????1.73 |
| ???4 | ?4.9 | ????1.53 |
| ???5 | ?5.1 | ????1.40 |
| ???6 | ?3.0 | ????0.87 |
| ???7 | ?4.9 | ????1.35 |
| ???8 | ?5.8 | ????2.3 |
| Comparative Examples 1 | ?3.8 | ????0.85 |
| ???9 | ?4.25 | ????1.40 |
| ???10 | ?4.35 | ????1.54 |
| ???11 | ?3.95 | ????1.56 |
| ???12 | ?3.10 | ????1.11 |
| ???13 | ?5.07 | ????1.97 |
| ???14 | ?9.20 | ????3.34 |
| ???15 | ?7.15 | ????2.44 |
| ???16 | ?8.05 | ????3.10 |
Claims (17)
1. non-volatility polymer electrolyte composition is characterized in that described polymer electrolyte composition contains:
A) at least a or multiple polyethylene oxide polymer, molecular weight is 200-4,000,000;
B) one or more an amount of ionic liquids, described ion liquid structure is: B+A-
Wherein,
B
+Be selected from: the indoles positively charged ion of the tetramethyleneimine positively charged ion of the pyrazoles positively charged ion of the glyoxaline cation of replacement, replacement, the piperidines positively charged ion of replacement, replacement, pyrroles's positively charged ion of replacement, replacement, carbazole positively charged ion, quaternary ammonium salt cationic, trialkyl sulfonium cation and the composition thereof of replacement;
A-is selected from: halide anion, tetrafluoride boron anion, phosphorus hexafluoride negatively charged ion, antimonic fluoride negatively charged ion, nitrate ion, trifluoromethyl sulfone ion, two (trifluoromethyl sulfone) amine negatively charged ion, hydrofluoric acid root negatively charged ion, hexafluoro tantalum negatively charged ion, hexafluoro niobium negatively charged ion and composition thereof;
The mass ratio of ionic liquid and polyethylene oxide polymer is 1: 9-6: 1;
C) randomly, the organic-or-inorganic salt that one or more are an amount of is selected from: lithium salts, sodium salt, sylvite, quaternary ammonium salt and composition thereof; Condition is not contain I when components b
-The time, this organic or inorganic salt is salt compounded of iodine, consumption is 0-20%, based on the gross weight of polymer dielectric;
D) randomly, the mineral filler that one or more are an amount of, consumption is 0-20%, based on the gross weight of polymer dielectric;
E) iodine is with the I that is contained among components b and the c
-Mol ratio be 1: 20-1: 2;
Condition is when amount of component b is not salt compounded of iodine, A
-Be I
-
2. the non-volatility polymer electrolyte composition in the claim 1, the molecular weight that it is characterized in that employed polyethylene oxide polymer is 350-4,000,000.
3. the non-volatility polymer electrolyte composition in the claim 1 or 2 is characterized in that glyoxaline cation and quaternary ammonium salt cationic and the composition thereof of employed ion liquid positively charged ion for replacing.
4. the non-volatility polymer electrolyte composition in the claim 1 or 3 is characterized in that the glyoxaline cation of employed ion liquid positively charged ion for replacing, and the structure of the glyoxaline cation of this replacement is as follows:
Wherein,
R
1For carbonatoms is the alkyl of 1-2;
R
2For carbonatoms is the alkyl of 2-16.
5. the non-volatility polymer electrolyte composition in the claim 4 is characterized in that R
2For carbonatoms is the alkyl of 2-10.
6. the non-volatility polymer electrolyte composition in the claim 4 or 5 is characterized in that R
2For carbonatoms is the alkyl of 3-6.
7. the non-volatility polymer electrolyte composition in the claim 1 is characterized in that employed ion liquid negatively charged ion is selected from halide anion: Cl
-, Br
-Perhaps I
-The tetrafluoride boron anion; Nitrate ion; Trifluoromethyl sulfone ion; Two (trifluoromethyl sulfone) amine negatively charged ion and composition thereof.
8. the non-volatility polymer electrolyte composition in the claim 1 or 7 is characterized in that employed ion liquid negatively charged ion is I
-The tetrafluoride boron anion; Two (trifluoromethyl sulfone) amine negatively charged ion.
9. the non-volatility polymer electrolyte composition in the claim 1, the mass ratio that it is characterized in that employed ionic liquid and employed polyethylene oxide polymer is 1: 4-4: 1.
10. the non-volatility polymer electrolyte composition in the claim 1, the mass ratio that it is characterized in that employed ionic liquid and employed polyethylene oxide polymer is 1: 2-4: 1.
11. the non-volatility polymer electrolyte composition in the claim 1 is characterized in that employed organic-or-inorganic salt is selected from lithium iodide, lithium perchlorate, trifluoromethyl sulfonic acid lithium, sodium iodide, potassiumiodide, ammonium iodide, tetraethyl ammonium iodide, tetrapropyl ammonium iodide, tetrabutylammonium iodide and composition thereof.
12. the non-volatility polymer electrolyte composition in the claim 1, it is characterized in that the mineral filler of using be the nanometer particle mineral filler: Nano titanium dioxide, silicon-dioxide, gama-alumina or γ-LiAlO
2
13. the non-volatility polymer electrolyte composition in the claim 1, the consumption that it is characterized in that employed mineral filler is 5-10%, based on the gross weight of polymer dielectric.
14. the non-volatility polymer electrolyte composition in the claim 1 is characterized in that the I that is contained among employed iodine and components b and the c
-Mol ratio be 1: 10-1: 5.
15. the preparation method of claim 1-14 non-volatility polymer electrolyte composition in each, key step is:
I) components b, c, d, e are joined respectively among the component a;
Ii) under 50-150 ℃ temperature condition, each component is mixed;
16. the preparation method of claim 1-14 non-volatility polymer electrolyte composition in each, described method comprises:
I) component d is being uniformly dispersed in the volatility anhydrous organic solvent under the agitation condition;
Ii) components b, c, e are joined in the above-mentioned suspension under agitation condition, mix;
Iii) component a is joined in the above-mentioned composition under agitation condition, be stirred to and dissolve fully and mix;
Organic solvent is volatilized fully.
17. the application of non-volatility polymer electrolyte composition in the dye sensitization nano-crystal thin-film solar cell in above-mentioned each claim.
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