CN100412129C - Method for preparing chemical crosslink gel lattice polymer electrolyte - Google Patents
Method for preparing chemical crosslink gel lattice polymer electrolyte Download PDFInfo
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- CN100412129C CN100412129C CNB2006100082878A CN200610008287A CN100412129C CN 100412129 C CN100412129 C CN 100412129C CN B2006100082878 A CNB2006100082878 A CN B2006100082878A CN 200610008287 A CN200610008287 A CN 200610008287A CN 100412129 C CN100412129 C CN 100412129C
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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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- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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Abstract
The invention relates to a manufacture method for electrolyte of dye sensitization TiO2 nanometer crystal porous membrane solar cell. It includes the following steps: mixing organic solvent containing inorganic iodine salt, iodine, and additive, or iron liquid electrolyte with 4-vinyl pyridine and the high molecule copolymer of acrylonitrile and crosslinking agent; directly coating onto TiO2 nanometer crystal film electrode surface; packaging with Pt sheet counter electrode or platinum carrying counter electrode to form cell, taking cross linking solidifying reacting while heating, the product would be gained. The invention has simple method, low viscosity of electrolyte before solidification reaction, and is benefit for improving cell photoelectric conversion efficiency.
Description
Technical field
The invention belongs to dye sensitization TiO
2The electrolytic solution preparing technical field of Na crystal porous membrane solar cell, the particularly preparation method of chemical crosslink gel lattice polymer electrolyte.
Background technology
Dye sensitization TiO
2The Na crystal porous membrane solar cell is a kind of novel solar battery of efficient, inexpensive, environmentally safe.The general employing of this battery contained I
-/ I
3 -The liquid electrolyte that redox couple, inorganic salt compounded of iodine, iodine and organic solvent are formed.But this electrolytic solution is revealed easily, and organic solvent is volatile, not only causes the cell sealing difficulty, and battery performance descends in the long term operation process, and shorten work-ing life.Substituting liquid electrolyte with solid electrolyte or electrolytic solution solid state is a kind of inexorable trend, because it can fundamentally improve the stability and the practicality of battery.Being subjected to the solid electrolyte that people pay much attention at present is gelatin polymer electrolytic solution, and wherein reporting more is the physical gel polyelectrolyte.It is that polymkeric substance passes through Intermolecular Forces, carries out crosslinked formed solid gel as Van der Waals force or hydrogen bond.But this electrolytic solution instability, because polymer melts or dissolving, electrolytic solution is become again liquid state again or is formed the isolating system of two-phase because of the polymer moiety crystallization makes it by solid-state under comparatively high temps.As document " A Solid State, Dye Sensitized Photoelectrochemical Cell ", F.Cao, G.Oskam, P.C.Searson, J.Phys.Chem.B.99 (1995), 17071~17073; " A novel gel polymerelectrolyte based on polyacrylonitrile (PAN) and its application in a solar cell ", M.A.K.L.Dissanayake, L.R.A.K. Bandara, R.S.P.Bokalawala, P.A.R.D.Jayathilaka, O.A.Ileperuma, S.Somasundaram, Mater.Res.Bull.37 (2002), 867~874 is disclosed.Yet, carry out the crosslinked chemically crosslinked gelatin polymer electrolytic solution that forms by chemical bond between macromolecular chain and have good thermostability, can the Yin Wendu rising not become liquid state again again, thereby have higher solvent hold facility.S.Yanagida people such as (Japan) adopts α-methacryloyl-ω-methoxyocta (oxyethylene) (MMO) to wait vinyl monomer to add linking agent to carry out in-situ cross-linked method and prepare the solid state battery that gelatin polymer electrolytic solution constitutes, though obtained 2.62% photoelectric transformation efficiency, but because polyreaction can not be carried out in the presence of iodine, make and the complicated process of preparation of battery be difficult to practicability.As document " Fabrication of Solid-State Dye-Sensitized TiO
2Solar Cell Using Polymer Electrolyte ", Bull.Chem.Soc.Jpn., 74 (2001), 387-393 is disclosed.Hayase (Japan) etc. are polymkeric substance with the poly 4 vinyl pyridine, halogenated alkane is that linking agent prepares the solid state battery that gelatin polymer electrolytic solution constitutes, though improved the thermostability of battery, crosslinking reaction also can be carried out under the situation that iodine exists simultaneously, but used linking agent occurs being separated in the electrolytic solution that contains organic solvents such as vinyl carbonate, propylene carbonate, and the affiliation that adds of additives such as lithium iodide, 4-tertiary butyl pyridine hinders gel formation, and the photoelectric transformation efficiency that is assembled into dye sensitization solar battery is lower.As document " Quasi-solid dye sensitized solar cells filled with phase-separatedchemically cross-linked ionic gels, Chem.Commun. ", 2003,1534-1535; " Additives for Increased Photoenergy Conversion Efficiencies of Quasi-Solid, Dye-Sensitized Solar Cells ", J.Electrochem.Soc., 152 (2005), A1105~A1108 is disclosed.
All above-mentioned documents here are incorporated herein by reference in full with it.
Summary of the invention
One object of the present invention is to overcome the deficiency of above-mentioned prior art, and a kind of preparation method of chemical crosslink gel lattice polymer electrolyte is provided.
Another object of the present invention provides high-molecular copolymer and the linking agent polyhalogenide that will contain 4-vinylpridine and vinyl cyanide mixes with organic solvent that contains inorganic salt compounded of iodine, iodine and additive or il electrolyte, prepares the method for chemical crosslink gel lattice polymer electrolyte under heating cured in place condition.
The present invention adopts the method for cured in place will contain the high-molecular copolymer of 4-vinylpridine and vinyl cyanide and the organic solvent or the ion liquid liquid electrolyte of linking agent polyhalogenide directly is applied to dye sensitization TiO
2The nano-crystal porous film electrode surface also is assembled into battery, and chemical crosslink reaction is carried out in heating at a certain temperature, makes the homogeneous chemistry cross linked gel network polymer electrolyte battery of Heat stability is good.Innovation part of the present invention is to use 4-vinylpridine and vinyl cyanide as high-molecular copolymer, and wherein contained pyridyl can be used for chemical crosslink reaction, can realize cured in place there being iodine to exist under the situation; Contained acrylonitrile group then can strengthen the consistency between each component, avoids occurring being separated.The dye sensitization solar battery that is assembled into described electrolytic solution easily encapsulates, and has higher photoelectric transformation efficiency.
The preparation method of chemical crosslink gel lattice polymer electrolyte of the present invention may further comprise the steps:
(1) inorganic salt compounded of iodine, iodine and different additive are dissolved in organic solvent or the ionic liquid make liquid electrolyte; Wherein, the concentration of inorganic salt compounded of iodine is 0.1~0.5 mol; The concentration of iodine in electrolytic solution is 0.05~0.5 mol; The concentration of additive in electrolytic solution is 0.1~0.4 mol;
(2) high-molecular copolymer with 4-vinylpridine and vinyl cyanide is dissolved in the liquid electrolyte of step (1) gained by a certain percentage, and wherein, high-molecular copolymer accounts for 2~5% of electrolytic solution total mass;
(3) a certain amount of linking agent polyhalogenide is joined in the electrolytic solution of step (2) gained; Wherein, the linking agent polyhalogenide accounts for 1~4% of electrolytic solution total mass;
(4) electrolytic solution of step (3) gained is stirred after, be coated in dye sensitization TiO
2The nano-crystal thin-film electrode surface, and with Pt sheet counter electrode or carry the platinum counter electrode and press thereon, under 60~80 ℃ of temperature, heat, be 1~4 hour heat-up time, cured in place obtains the dye sensitization TiO that is used for of the present invention
2The chemical crosslink gel lattice polymer electrolyte of nano-crystal thin-film battery.
Described inorganic salt compounded of iodine is selected from a kind of in lithium iodide, sodium iodide, the potassiumiodide.
Described additive is selected from 4-tertiary butyl pyridine, 2-propyl group pyridine, 2, a kind of in 2 '-dipyridyl, the benzoglyoxaline.
The structure of the high-molecular copolymer of described 4-vinylpridine and vinyl cyanide is as follows:
Wherein, x: y is 1: 1~1: 3.
Described linking agent polyhalogenide is selected from alkylene dihalide, polymer dihalide or aromatic halides.Wherein, the saturated dihalide hydrocarbon structure is as follows:
XCH
2(CH
2)
nCH
2(n is 2~6 to X; X is Cl, Br or I);
The polymer dihalide is I (CH
2CH
2O)
mCH
2CH
2I m is 1~8, and preferred molecular weight is 370~620;
Aromatic halides is 1,2,4,5-tetrabromo methylbenzene or 1,4-xylylene bromide.
Organic solvent in the described organic solvent liquid electrolytic solution is selected from one or more the mixture in vinyl carbonate, propylene carbonate, acetonitrile, the 3-methoxypropionitrile, is preferably the mixture of vinyl carbonate and propylene carbonate; Wherein, vinyl carbonate: the volume ratio of propylene carbonate is 5: 5~8: 2, is preferably 5: 5.
The glyoxaline cation of ion liquid positively charged ion in the described il electrolyte for replacing, the structure of the glyoxaline cation of this replacement is as follows:
Wherein:
R
1Alkyl for carbonatoms 1~2; R
2For the alkyl of carbonatoms 2~10 or be the oligomerisation ethylene oxide group of molecular weight between 60~2000.
Employed ion liquid negatively charged ion is selected from halide anion (Cl
-, Br
-Perhaps I
-), tetrafluoride boron anion, nitrate ion, trifluoromethyl sulfone ion or two (trifluoromethyl sulfone) amine negatively charged ion.
Described ionic liquid is single ionic liquid or different kinds of ions mixtures of liquids.
The present invention adopts the cured in place technology to prepare chemical crosslink gel lattice polymer electrolyte, and method is simple, and is with low cost.Electrolytic solution viscosity before the curing reaction is little, and the liquid electrolyte that contains high-molecular copolymer and chemical cross-linking agent before not only helping solidifying can fully penetrate into TiO
2In the Na crystal porous membrane, form the good interface contact, help the raising of cell photoelectric efficiency of conversion; And curing reaction post polymerization thing electrolytic solution forms immobilising solid, can not undergo phase transition reverse because of envrionment temperature raises after the curing, become liquid state heavily again, improved the thermostability and the practicality of battery greatly.
The present invention will be illustrated by the following examples.But, be to be understood that the present invention is not limited to particular example described here 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.
The subordinate list explanation: table 1 is to use chemical crosslink gel lattice polymer electrolyte of the present invention and dye sensitization TiO
2Nano-crystal porous film electrode, the photoelectric properties of the dye sensitization solar battery of Pt counter electrode assembling.
Measuring method: with the chemical crosslink gel lattice polymer electrolyte of the present invention preparation as electrolytic solution, dye sensitization TiO
2Nano-crystal porous film electrode is as working electrode, and Pt sheet or year platinum electrode are assembled into dye sensitization solar battery and carry out the photoelectric properties measurement as counter electrode.
(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 xenon lamp of 500W, 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
Embodiment 1
With the 0.0648g potassiumiodide, 0.0099g iodine joins in the 1.0000g propylene carbonate and makes liquid electrolyte.Add the high-molecular copolymer of 0.0300g4-vinyl pyridine and vinyl cyanide earlier, add 0.0150g two iodohexanes after the dissolving again, after stirring, be coated in dye sensitization TiO
2The nano-crystal porous film electrode surface, and press with Pt sheet counter electrode and to be assembled into battery thereon, place 75 ℃ of baking ovens to be heating and curing then 2 hours, obtain the dye sensitization TiO that on-the-spot chemical crosslink gel lattice polymer electrolyte of the present invention is assembled into
2The nano-crystal thin-film battery.
Embodiment 2
Except 1.0000g propylene carbonate in the step (1) is become the mixture of 1.0000g vinyl carbonate and propylene carbonate (volume ratio is 5: 5), other step and processing condition are identical with embodiment 1, obtain the dye sensitization TiO that on-the-spot chemical crosslink gel lattice polymer electrolyte of the present invention is assembled into
2The nano-crystal thin-film battery.
Embodiment 3
Carry the platinum counter electrode except Pt sheet counter electrode in the step (4) is become, other step and processing condition are identical with embodiment 2, obtain the dye sensitization TiO that on-the-spot chemical crosslink gel lattice polymer electrolyte of the present invention is assembled into
2The nano-crystal thin-film battery.
Embodiment 4
Except 0.0150g two iodohexanes in the step (3) are become 0.0275g I (CH
2CH
2O)
mCH
2CH
2Outside the I (molecular weight is 620), other step and processing condition are identical with embodiment 2, obtain the dye sensitization TiO that on-the-spot chemical crosslink gel lattice polymer electrolyte of the present invention is assembled into
2The nano-crystal thin-film battery.
Embodiment 5
0.0552g iodine joined in 1.0000g1-methyl-3-hexyl imidazoles iodide ion liquid make liquid electrolyte.Add the high-molecular copolymer of 0.0400g4-vinyl pyridine and vinyl cyanide earlier, add 0.0200g two iodohexanes after the dissolving again, after stirring, be coated in dye sensitization TiO
2The nano-crystal porous film electrode surface, and press with Pt sheet counter electrode and to be assembled into battery thereon, place 75 ℃ of baking ovens to be heating and curing then 3 hours, obtain the dye sensitization TiO that on-the-spot chemical crosslink gel lattice polymer electrolyte of the present invention is assembled into
2The nano-crystal thin-film battery.
Embodiment 6
Except increasing the 0.0097g lithium iodide in step (1), other step and processing condition are identical with embodiment 5, obtain the dye sensitization TiO that on-the-spot chemical crosslink gel lattice polymer electrolyte of the present invention is assembled into
2The nano-crystal thin-film battery.
Embodiment 7
Except in step (1), increasing 0.2000g1-methyl-3-fluoroethane borate, and the amount of 1-methyl-3-hexyl imidazoles iodine is reduced to outside the 0.8000g by 1.0000g, other step and processing condition are identical with embodiment 5, obtain the dye sensitization TiO that on-the-spot chemical crosslink gel lattice polymer electrolyte of the present invention is assembled into
2The nano-crystal thin-film battery.
Embodiment 8
Except increasing the 0.0097g lithium iodide in step (1), other step and processing condition are identical with embodiment 7, obtain the dye sensitization TiO that on-the-spot chemical crosslink gel lattice polymer electrolyte of the present invention is assembled into
2The nano-crystal thin-film battery.
Embodiment 9
Except 0.0200g two iodohexanes in the step (3) are become the 0.0128g dibromobutane, other step and processing condition are identical with embodiment 5, obtain the dye sensitization TiO that on-the-spot chemical crosslink gel lattice polymer electrolyte of the present invention is assembled into
2The nano-crystal thin-film battery.
Embodiment 10
Except increase 0.0098g4-tertiary butyl pyridine in step (1), other step and processing condition are identical with embodiment 6, obtain the dye sensitization TiO that on-the-spot chemical crosslink gel lattice polymer electrolyte of the present invention is assembled into
2The nano-crystal thin-film battery.
Embodiment 11
Except the 0.0098g4-tertiary butyl pyridine in the step (1) is become the 0.0088g2-propyl group pyridine, other step and processing condition are identical with embodiment 10, obtain the dye sensitization TiO that on-the-spot chemical crosslink gel lattice polymer electrolyte of the present invention is assembled into
2The nano-crystal thin-film battery.
Embodiment 12
Except the 0.0098g4-tertiary butyl pyridine in the step (1) is become 0.0139g2, outside 2 '-dipyridyl, other step and processing condition are identical with embodiment 10, obtain the dye sensitization TiO that on-the-spot chemical crosslink gel lattice polymer electrolyte of the present invention is assembled into
2The nano-crystal thin-film battery.
Table I
Embodiment | Short-circuit photocurrent Isc (mA cm-2) | Open circuit photovoltage Voc (V) | Fill factor, curve factor FF | Photoelectric transformation efficiency η (%) |
1 | 14.65 | 0.645 | 0.65 | 6.17 |
2 | 14.75 | 0.670 | 0.66 | 6.53 |
3 | 9.75 | 0.678 | 0.58 | 3.86 |
4 | 17.55 | 0.590 | 0.57 | 5.95 |
5 | 13.40 | 0.598 | 0.62 | 5.0 |
6 | 15.10 | 0.606 | 0.60 | 5.45 |
7 | 13.25 | 0.598 | 0.59 | 4.71 |
8 | 14.10 | 0.586 | 0.60 | 4.92 |
9 | 11.65 | 0.600 | 0.62 | 4.37 |
10 | 14.45 | 0.616 | 0.60 | 5.31 |
11 | 12.30 | 0.658 | 0.60 | 4.88 |
12 | 13.35 | 0.636 | 0.63 | 5.38 |
Claims (8)
1. the preparation method of a chemical crosslink gel lattice polymer electrolyte is characterized in that, this method may further comprise the steps:
(1) inorganic salt compounded of iodine, iodine and additive are dissolved in organic solvent or the ionic liquid make liquid electrolyte; Wherein, the concentration of inorganic salt compounded of iodine in electrolytic solution is 0.1~0.5 mol; The concentration of iodine is 0.05~0.5 mol; The concentration of additive in electrolytic solution is 0.1~0.4 mol;
(2) high-molecular copolymer with 4-vinylpridine and vinyl cyanide is dissolved in the liquid electrolyte of step (1) gained, and wherein, high-molecular copolymer accounts for 2~5% of electrolytic solution total mass;
(3) the linking agent polyhalogenide is joined in the electrolytic solution of step (2) gained; Wherein, the linking agent polyhalogenide accounts for 1~4% of electrolytic solution total mass;
(4) electrolytic solution of step (3) gained is stirred after, be coated in dye sensitization TiO
2The nano-crystal thin-film electrode surface, and with Pt sheet counter electrode or carry the platinum counter electrode and press thereon, under 60~80 ℃ of temperature, heat, make the on-site crosslinked curing of electrolytic solution of step (3) gained, obtain being used for dye sensitization TiO
2The chemical crosslink gel lattice polymer electrolyte of nano-crystal thin-film battery;
Described additive is selected from 4-tertiary butyl pyridine, 2-propyl group pyridine, 2, a kind of in 2 '-dipyridyl or the benzoglyoxaline;
Described linking agent polyhalogenide is selected from alkylene dihalide, polymer dihalide or aromatic halides; Wherein:
The saturated dihalide hydrocarbon structure is:
XCH
2(CH
2)
nCH
2X, n are 2~6; X is Cl, Br or I;
The polymer dihalide is I (CH
2CH
2O)
mCH
2CH
2I, m are 1~8;
Aromatic halides is 1,2,4,5-tetrabromo methylbenzene or 1,4-xylylene bromide.
2. method according to claim 1 is characterized in that: described inorganic salt compounded of iodine is selected from a kind of in lithium iodide, sodium iodide or the potassiumiodide.
4. method according to claim 1 is characterized in that: described organic solvent is selected from one or more the mixture in vinyl carbonate, propylene carbonate, acetonitrile, the 3-methoxypropionitrile.
5. method according to claim 4 is characterized in that: the volume ratio of the mixture of described vinyl carbonate and propylene carbonate is 5: 5~8: 2.
6. method according to claim 1 is characterized in that: the glyoxaline cation of described ion liquid positively charged ion for replacing, and the structure of the glyoxaline cation of this replacement is:
Wherein:
R
1Alkyl for carbonatoms 1~2; R
2For the alkyl of carbonatoms 2~10 or be the oligomerisation ethylene oxide group of molecular weight between 60~2000;
Described ion liquid negatively charged ion is selected from Cl
-, Br
-, I
-, tetrafluoride boron anion, nitrate ion, trifluoromethyl sulfone ion or two (trifluoromethyl sulfone) amine negatively charged ion.
7. method according to claim 6 is characterized in that: described ionic liquid is single ionic liquid or different kinds of ions mixtures of liquids.
8. method according to claim 1 is characterized in that: be 1~4 hour described heat-up time.
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JP5481171B2 (en) * | 2009-11-18 | 2014-04-23 | 株式会社林技術研究所 | Photocrosslinkable electrolyte composition and dye-sensitized solar cell |
CN101840793A (en) * | 2010-04-29 | 2010-09-22 | 株洲日望电子科技有限公司 | Super capacitor and preparation method thereof |
CN105914401A (en) * | 2016-06-27 | 2016-08-31 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium ion battery containing same |
CN109887764B (en) * | 2019-01-24 | 2021-06-25 | 无锡凯帕德瑞科技有限公司 | Electrolyte of high-nickel ternary system capacitor battery and preparation method thereof |
CN110364363B (en) * | 2019-07-08 | 2021-08-24 | 江苏理工学院 | Preparation method of dye-sensitized solar cell |
CN114835854A (en) * | 2022-06-10 | 2022-08-02 | 中国科学院兰州化学物理研究所 | Ionic liquid copolymer and method for preparing cyclic carbonate by using same |
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