CN103021667A - In-situ chemical crosslinking gel electrolyte for dye-sensitized solar cells and production method thereof - Google Patents
In-situ chemical crosslinking gel electrolyte for dye-sensitized solar cells and production method thereof Download PDFInfo
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- CN103021667A CN103021667A CN2012105811314A CN201210581131A CN103021667A CN 103021667 A CN103021667 A CN 103021667A CN 2012105811314 A CN2012105811314 A CN 2012105811314A CN 201210581131 A CN201210581131 A CN 201210581131A CN 103021667 A CN103021667 A CN 103021667A
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- 239000011245 gel electrolyte Substances 0.000 title claims abstract description 28
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 238000010382 chemical cross-linking Methods 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000003792 electrolyte Substances 0.000 claims abstract description 23
- 239000004814 polyurethane Substances 0.000 claims abstract description 16
- 229920002635 polyurethane Polymers 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 13
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 9
- 239000011244 liquid electrolyte Substances 0.000 claims description 25
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 23
- 239000011630 iodine Substances 0.000 claims description 23
- 229910052740 iodine Inorganic materials 0.000 claims description 23
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 238000002347 injection Methods 0.000 claims description 15
- 239000007924 injection Substances 0.000 claims description 15
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 12
- 239000012528 membrane Substances 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000012948 isocyanate Substances 0.000 claims description 8
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 230000018044 dehydration Effects 0.000 claims description 7
- 238000006297 dehydration reaction Methods 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229920002545 silicone oil Polymers 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 235000009518 sodium iodide Nutrition 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 4
- IFVTZJHWGZSXFD-UHFFFAOYSA-N biphenylene Chemical group C1=CC=C2C3=CC=CC=C3C2=C1 IFVTZJHWGZSXFD-UHFFFAOYSA-N 0.000 claims description 3
- 125000005442 diisocyanate group Chemical group 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000005518 polymer electrolyte Substances 0.000 claims description 3
- GTACSIONMHMRPD-UHFFFAOYSA-N 2-[4-[2-(benzenesulfonamido)ethylsulfanyl]-2,6-difluorophenoxy]acetamide Chemical compound C1=C(F)C(OCC(=O)N)=C(F)C=C1SCCNS(=O)(=O)C1=CC=CC=C1 GTACSIONMHMRPD-UHFFFAOYSA-N 0.000 claims description 2
- 101710130081 Aspergillopepsin-1 Proteins 0.000 claims description 2
- 102100031007 Cytosolic non-specific dipeptidase Human genes 0.000 claims description 2
- 206010070834 Sensitisation Diseases 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- XQSFXFQDJCDXDT-UHFFFAOYSA-N hydroxysilicon Chemical compound [Si]O XQSFXFQDJCDXDT-UHFFFAOYSA-N 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 239000005056 polyisocyanate Substances 0.000 claims description 2
- 229920001228 polyisocyanate Polymers 0.000 claims description 2
- 230000008313 sensitization Effects 0.000 claims description 2
- -1 bipyridyl ruthenium Chemical compound 0.000 claims 2
- 239000000446 fuel Substances 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- 229920001002 functional polymer Polymers 0.000 abstract 1
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 238000006068 polycondensation reaction Methods 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 16
- 230000005611 electricity Effects 0.000 description 11
- 239000002243 precursor Substances 0.000 description 10
- 239000002202 Polyethylene glycol Substances 0.000 description 8
- 229920001223 polyethylene glycol Polymers 0.000 description 8
- 238000005286 illumination Methods 0.000 description 7
- 238000004088 simulation Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 239000006193 liquid solution Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000005538 encapsulation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention belongs to the field of functional polymers and relates to in-situ chemical crosslinking gel electrolyte for dye-sensitized solar cells and a production method thereof. Polyurethane polymer is typically a polycondensation product. Prepolymer electrolyte solution of the polyurethane polymer is able to polymerize in situ in the dye-sensitized solar cells so as to form polymer gel electrolyte. Prepolymer solution of the gel electrolyte is well contacted with a TiO2 electrode. Cell conversion efficiency is high. The problems of cell packaging and easiness in electrolyte leakage are also solved. The in-situ chemical crosslinking gel electrolyte for dye-sensitized solar cells has promising application prospect in the field of dye-sensitized solar cells.
Description
Technical field
The present invention relates to a kind of in-situ chemical cross-linked gel electrolyte for DSSC, belong to the battery material field, the invention still further relates to this in-situ chemical cross-linked gel electrolyte preparation method.
Background technology
M Gr tzel group development in 1991 novel dye sensitized nano crystal salar battery, be called for short DSSC, for new road (" A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO have been opened up in the development of solar cell
2Films ". Brain O ' Regan and Michael Gr tzel. Nature, 1991,353:737-740. is based on the colloid TiO of dye sensitization
2The low cost of film, high efficiency solar cell, " nature " magazine, 1991).
DSSC has caused and has paid close attention to widely and study, and obtained good progress owing to manufacture method is simple, with low cost, the higher strong competitor who becomes the traditional silicon solar cell of conversion efficiency.But the liquid electrolyte existence and stability that its uses is poor, the encapsulation difficulty, leak the problems such as volatilization and battery life be short easily, thereby has reduced practicality, is unfavorable for the industrialization of DSSC.Also useful solid electrolyte for this reason, but its conductivity is lower, and and TiO
2The contact of electrode surface is bad, and electrolyte is difficult for permeating in the hole, causes the efficient of solid state battery not high.
For overcoming problem liquid and that solid electrolyte exists, quasi-solid electrolyte is flourish.
Two kinds of methods are arranged when preparing quasi-solid-state dye sensitized solar cell by polymer gel electrolyte, and the not yet crosslinked electrolyte that ⑴ can contain crosslinking agent by injection then causes the crosslinked gel that becomes of electrolyte, i.e. in-situ polymerization between two electrodes; ⑵ also can prepare first polymer gel electrolyte, and it is pressed in middle and forms quasi-solid-state dye sensitized solar cell with two electrode handles.During by second method assembling DSSC, because larger viscosity and the volume of polymer dielectric is difficult to and TiO
2The close contact of film, so the electricity conversion of battery is lower, (100mW/cm about 5%
2).And in-situ polymerization is lower owing to the viscosity of performed polymer (or oligomer) electrolyte solution, and molecule is less, can be penetrated into TiO fully
2Then the inside of film carry out crosslinked, curing under certain condition, can guarantee electrolyte and TiO
2The film close contact.The size of polymer molecular chain is that molecular weight can be unrestricted simultaneously, suitably increases, and being conducive to increases the ability that polymer molecule absorbs, locks liquid electrolyte, and improves its mechanical performance.Therefore can bring up to (100mW/cm more than 6% by the accurate solid-state DSSC electricity conversion of in-situ polymerization assembling
2).
Summary of the invention
Purpose of the present invention provides a kind of higher conductivity that has for the shortcoming that overcomes above-mentioned prior art existence with deficiency just, with TiO
2The contact of electrode surface is good, and conversion efficiency is high, solves again the encapsulation of battery and the gel electrolyte that is used for DSSC of the problem that electrolyte is easily revealed, thereby can realize the industrialization of DSSC.
The present invention also provides the preparation method of this gel electrolyte.
The objective of the invention is to realize by following technical proposal:
But a kind of gel electrolyte of the in-situ solidifying for DSSC, it forms precursor solution by liquid electrolyte and the polymer that is dissolved in liquid electrolyte, be injected among the DSSC DSSC, under certain condition, precursor solution is crosslinked, solidify to form gel electrolyte, and forms accurate solid-state DSSC.
Described liquid electrolyte forms the I of salt compounded of iodine by salt compounded of iodine (KI, sodium iodide, lithium iodide, tetrabutylammonium iodide) and iodine and organic solvent
-Molar concentration is the 0.1-1 mol/L, the I of iodine
3 -Molar concentration be the 0.01-0.1 mol/L,
Described polymer is by isocyanates (toluene di-isocyanate(TDI) TDI, hexamethylene diisocyanate HDI, IPDI IPDI, methyl diphenylene diisocyanate MDI etc.) and binary (or polynary) alcohol, makes through polyaddition reaction progressively such as PPG, PEPA, alkane hydroxy silicon oil, hydroxy polyethers silicone oil etc.
Described organic solvent is one or both or the two or more combination in GBL, vinyl carbonate, propylene carbonate, acetonitrile, dimethyl carbonate or the diethyl carbonate.
The preparation method of gel electrolyte and accurate solid-state DSSC, carry out in the steps below:
(a) with KI (or lithium iodide, sodium iodide, tetrabutylammonium iodide) and iodine organic solvent dissolution, make the I of KI
-Molar concentration is the I of 0.1-1 mol/L and iodine
3 -Molar concentration be the 0.01-0.1 mol/L, its organic solvent is 1-METHYLPYRROLIDONE, 1, one or both of 4-butyrolactone, vinyl carbonate, propylene carbonate, acetonitrile, dimethyl carbonate or diethyl carbonate or two or more being combined mix, and obtain liquid electrolyte;
(b) with employed polyalcohol at 110 ℃～120 ℃, vacuum pressure is under the 0.13KPa, the dehydration 2h about.When cooling to 40 ℃～50 ℃, add the liquid electrolyte for preparing, after mixing, drip the polyisocyanates that measures, continue to mix.The weight ratio of performed polymer and liquid electrolyte is 1:2～10;
(c) will be in advance at 5 * 10-4molL
-1Bipyridyl ruthenium dye (RuL
2(NCS)
2: soaked 12 hours nanocrystalline porous TiO in ethanol solution 2TBA)
2Membrane electrode takes out, and dries up, will be modified with again platinum to electrode surface down with TiO
2The electrode alignment is clamped battery with clip.120 ℃ of lower 15min that place around then sealing with the heat-seal film, are injected into TiO with the above-mentioned electrolyte solution of preparing again in vacuum drying oven
2Between membrane electrode and the platinum electrode, injection is put in battery in the vacuum drying oven after finishing, under (80 ± 10) ℃, insulation 2h, make electrolyte solution generation complete reaction, form the polyurethane gle electrolyte, room temperature to be dropped to namely gets quasi-solid-state dye sensitized solar cell.
The present invention is by being directly injected into TiO with polymer dielectric solution (being precursor solution)
2Between electrode and the Pt electrode, prepolymer continues to react under 70-90 ℃ of condition, and liquid electrolyte is fixed among the derivatized polymers, forms gel electrolyte.The present invention has further solved viscosity larger when gel-form solid polymer electrolyte is used in the dye-sensitized cell field and volume is difficult to and TiO
2The problem of the close contact of film has further improved the electricity conversion based on the DSSC of gel electrolyte.
The gel electrolyte of above-mentioned preparation is used for DSSC, at 100 mW/cm
2(AM1.5) under the illumination simulation, its short circuit current, open circuit voltage, fill factor, curve factor, electricity conversion are respectively 10.47-18.68mAcm
-2, 625-679mV, 0.5214-0.6124,4.20-6.57%.
Dyestuff in the described DSSC is for containing ruthenium dye N719.
Light anode in the described DSSC is nano-TiO
2Film.
Time in the described DSSC,, very Pt was to electrode.
Have following advantage and effect owing to take technique scheme to make the technology of the present invention and oneself have technology to compare:
(a) polyurethane and series copolymer thereof or blend are suitable as the gel electrolyte of DSSC very much.Its distinctive two phase structure makes gel electrolyte not only have good mechanical property but also have higher ionic conductivity; The cementitiousness that it is good particularly to metal and glass, is conducive to improve gel electrolyte and TiO
2Film and to the interface combination of electrode;
(b) the present invention is used for this class electrolyte of DSSC, and raw material is easy to get, and preparation process is simple, and prepared polybenzazole precursor liquid solution can be directly injected between battery two electrodes, improves and electrolyte TiO
2The contact of film, gel electrolyte can effectively solve the encapsulation problem of dye-sensitized cell, has simultaneously desirable electricity conversion, has good application prospect in field of dye-sensitized solar cells;
(c) gel electrolyte of preparation is used for DSSC, at 100 mW/cm
2(AM1.5) under the illumination simulation, its short circuit current, open circuit voltage, fill factor, curve factor, electricity conversion are respectively 10.47-18.68mAcm
-2, 625-679mV, 0.5214-0.6124,4.20-6.57%.
Embodiment
Embodiment 1
KI 33.2g and iodine 5.08 g are dissolved with GBL 1000mL, make the I of KI
-Molar concentration is the I of 0.2 mol/L and iodine
3 -Molar concentration be 0.02 mol/L, obtain liquid electrolyte; The polyethylene glycol (molecular weight is 10000) that takes by weighing 10g places flask, and at 110 ℃～120 ℃, vacuum pressure is under the 0.13KPa, about dehydration 2h.When cooling to 40 ℃～50 ℃, pass into nitrogen, add the liquid electrolyte 100g for preparing, mix, drip 1.22g toluene di-isocyanate(TDI) (TDI), continue to mix, obtain polyurethane gle electrolyte precursor liquid solution, be flow regime.Then will be in advance 5 * 10
-4MolL
-1Bipyridyl ruthenium dye (RuL
2(NCS)
2: soaked 12 hours nanocrystalline porous TiO in ethanol solution 2TBA)
2Membrane electrode takes out, and is dry with the absolute ethyl alcohol flushing, with TiO
2Electrode film faces up and is placed on the clean experimental bench, the punching that will totally be modified with again platinum to electrode surface down with TiO
2Alignment is that two sheet glass stagger slightly, reserves the wide current-carrying part of about 4mm as battery testing usefulness, with clip battery is clamped.Be put in 120 ℃ of lower 15min of placement in the vacuum drying oven, around then sealing with the heat-seal film, reserve injection orifice, the more above-mentioned polyurethane gle electrolyte precursor injection of solution of preparing is entered TiO
2Between membrane electrode and the platinum electrode, with the injection orifice sealing, battery was put in the vacuum drying oven after injection was finished, and at 75 ℃ of lower reaction 2h, electrolyte solution reacts and forms the polyurethane gle electrolyte, obtains quasi-solid-state dye sensitized solar cell.This battery is at 100 mW/cm
2(AM1.5) under the illumination simulation, short circuit current, open circuit voltage, fill factor, curve factor, electricity conversion are respectively 10.47mAcm
-2, 655mV, 0.6124,4.20%.
Embodiment 2
Lithium iodide 40.1g and iodine 7.61g are dissolved with vinyl carbonate and each 500mL of propylene carbonate, make the I of KI
-Molar concentration is the I of 0.3 mol/L and iodine
3 -Molar concentration be 0.03 mol/L, obtain liquid electrolyte; Take by weighing polyethylene glycol (molecular weight is 6000) 15g 80 ℃ of lower fusings, add the 2.5g adipic acid and under 80 ℃, react to each other, add again the 0.8g trimethylolpropane after the reaction 2h, continue after the reaction 2h, under 120 ℃, vacuum pressure is under the 0.13KPa, about dehydration 2h.When cooling to 50 ℃, drip the hexamethylene diisocyanate HDI 1.95g that measures, slowly heat up, be stabilized in 80 ℃ of lower continuation and react, when viscosity increases, add the liquid electrolyte 90g for preparing, obtain polyurethane gle electrolyte precursor liquid solution, be flow regime.Then will be in advance 5 * 10
-4MolL
-1Bipyridyl ruthenium dye (RuL
2(NCS)
2: soaked 12 hours nanocrystalline porous TiO in ethanol solution 2TBA)
2Membrane electrode takes out, and is dry with the absolute ethyl alcohol flushing, with TiO
2Electrode film faces up and is placed on the clean experimental bench, the punching that will totally be modified with again platinum to electrode surface down with TiO
2Alignment is that two sheet glass stagger slightly, reserves the wide current-carrying part of about 4mm as battery testing usefulness, with clip battery is clamped.Be put in 120 ℃ of lower 15min of placement in the vacuum drying oven, around then sealing with the heat-seal film, reserve injection orifice, the more above-mentioned polyurethane gle electrolyte precursor injection of solution of preparing is entered TiO
2Between membrane electrode and the platinum electrode, with the injection orifice sealing, battery was put in the vacuum drying oven after injection was finished, and at 80 ℃ of lower reaction 2h, electrolyte solution reacts and forms the polyurethane gle electrolyte, obtains quasi-solid-state dye sensitized solar cell.This battery is at 100 mW/cm
2(AM1.5) under the illumination simulation, short circuit current, open circuit voltage, fill factor, curve factor, electricity conversion are respectively 14.54mAcm
-2, 679mV, 0.5721,5.65%.
Embodiment 3
Sodium iodide 75g and iodine 12.69 g are dissolved with acetonitrile 400 mL, dimethyl carbonate 600mL, make the I of KI
-Molar concentration is the I of 0.5 mol/L and iodine
3 -Molar concentration be 0.05 mol/L, obtain liquid electrolyte; At 110 ℃, vacuum pressure is under the 0.13KPa with employed polyethylene glycol (molecular weight is 20000) 20.0g, about dehydration 2h.Silicone oil (hydroxy radical content 15-35) 15g and calculating methyl diphenylene diisocyanate MDI 12.6g well react under 75 ℃ of oil bath conditions, stir; Then add the polyethylene glycol that has dewatered and finished; It is thick that the question response thing becomes white, adds the 110g liquid electrolyte, fully stirs, and reacts to add the 5g trimethylolpropane in two hours, obtains polyurethane gle electrolyte precursor liquid solution, is flow regime.Then will be in advance 5 * 10
-4MolL
-1Bipyridyl ruthenium dye (RuL
2(NCS)
2: soaked 12 hours nanocrystalline porous TiO in ethanol solution 2TBA)
2Membrane electrode takes out, and is dry with the absolute ethyl alcohol flushing, with TiO
2Electrode film faces up and is placed on the clean experimental bench, the punching that will totally be modified with again platinum to electrode surface down with TiO
2Alignment is that two sheet glass stagger slightly, reserves the wide current-carrying part of about 4mm as battery testing usefulness, with clip battery is clamped.Be put in 120 ℃ of lower 15min of placement in the vacuum drying oven, around then sealing with the heat-seal film, reserve injection orifice, the more above-mentioned polyurethane gle electrolyte precursor injection of solution of preparing is entered TiO
2Between membrane electrode and the platinum electrode, with the injection orifice sealing, battery was put in the vacuum drying oven after injection was finished, and at 80 ℃ of lower reaction 2h, electrolyte solution reacts and forms the polyurethane gle electrolyte, obtains quasi-solid-state dye sensitized solar cell.This battery is at 100 mW/cm
2(AM1.5) under the illumination simulation, short circuit current, open circuit voltage, fill factor, curve factor, electricity conversion are respectively 16.31mAcm
-2, 665mV, 0.5336,5.79%.
Embodiment 4
Tetrabutylammonium iodide 258.2g and iodine 17.77 g are dissolved with GBL, each 500mL of propylene carbonate, make the I of KI
-Molar concentration is the I of 0.7 mol/L and iodine
3 -Molar concentration be 0.07 mol/L, obtain liquid electrolyte; At 110 ℃, vacuum pressure is under the 0.13KPa with employed polyethylene glycol (molecular weight is 2000) 20g, about dehydration 2h.
Silicone oil (hydroxy radical content 15-35) 15g and calculating isocyanates IPDI 13.5g well react under 75 ℃ of oil bath conditions, stir; Then add the polyethylene glycol that has dewatered and finished; It is thick that the question response thing becomes white, adds the 150g liquid electrolyte, fully stirs, react and added the 5g trimethylolpropane in two hours, treat that flowability reduces, have certain viscosity, do not descend stream mode namely to obtain the polyurethane gle electrolyte until beaker is inverted electrolyte.By the quasi-solid-state dye sensitized solar cell of its assembling at 100 mW/cm
2(AM1.5) under the illumination simulation, short circuit current, open circuit voltage, fill factor, curve factor, electricity conversion are respectively 18.68mAcm
-2, 625mV, 0.5624,6.57%.
Embodiment 5
KI 166g and iodine 25.38 g are dissolved with diethyl carbonate 400mL, dimethyl carbonate 400mL, vinyl carbonate 200ml, make the I of KI
-Molar concentration is the I of 1.0 mol/L and iodine
3 -Molar concentration be 0.1 mol/L, obtain liquid electrolyte; At 110 ℃, vacuum pressure is under the 0.13KPa with employed polyethylene glycol (molecular weight is 2000) 20g, about dehydration 2h.Silicone oil (hydroxy radical content 15-35) 15g and calculating isocyanates IPDI 13.5g well react under 75 ℃ of oil bath conditions, stir; Then add the polyethylene glycol that has dewatered and finished; It is thick that the question response thing becomes white, adds the 100g liquid electrolyte, fully stirs, react and added the 5g trimethylolpropane in two hours, treat that flowability reduces, have certain viscosity, do not descend stream mode namely to obtain the polyurethane gle electrolyte until beaker is inverted electrolyte.By the quasi-solid-state dye sensitized solar cell of its assembling at 100 mW/cm
2(AM1.5) under the illumination simulation, short circuit current, open circuit voltage, fill factor, curve factor, electricity conversion are respectively 13.78mAcm
-2, 635mV, 0.5214,4.56%.
Claims (5)
1. but a gel electrolyte that is used for the in-situ solidifying of DSSC comprises liquid electrolyte and prepolymer, it is characterized in that: described liquid electrolyte forms the I of salt compounded of iodine by salt compounded of iodine and iodine and organic solvent
-Molar concentration is the 0.1-1 mol/L, the I of iodine
3 -Molar concentration be the 0.01-0.1 mol/L, described prepolymer by isocyanates and binary or polyalcohol through polyaddition reaction progressively and make; The weight ratio of prepolymer and liquid electrolyte is 1:2～10.
2. but the gel electrolyte of the in-situ solidifying for the fuel sensitization solar battery according to claim 1 is characterized in that: described salt compounded of iodine is a kind of in KI, lithium iodide, sodium iodide, the tetrabutylammonium iodide; Described organic solvent is one or both or the two or more combination in GBL, vinyl carbonate, propylene carbonate, acetonitrile, dimethyl carbonate or the diethyl carbonate.
3. but the gel electrolyte of the in-situ solidifying for DSSC according to claim 1 is characterized in that: described isocyanates is a kind of among toluene di-isocyanate(TDI) TDI, hexamethylene diisocyanate HDI, IPDI IPDI, the methyl diphenylene diisocyanate MDI etc.; Described binary or polyalcohol are one or both in PPG, PEPA, alkane hydroxy silicon oil, the hydroxy polyethers silicone oil.
4. but the preparation method of the gel electrolyte of the described in-situ solidifying for DSSC of a claim 1-3 is characterized in that it carries out in the steps below:
(a) with KI and iodine organic solvent dissolution, make the I of KI
-Molar concentration is the I of 0.1-1 mol/L and iodine
3 -Molar concentration be the 0.01-0.1 mol/L, its organic solvent is that one or both or two or more being combined of GBL, vinyl carbonate, propylene carbonate, acetonitrile, dimethyl carbonate or diethyl carbonate mixes, and obtains liquid electrolyte;
(b) with employed polyalcohol at 110 ℃～120 ℃, vacuum pressure is under the 0.13KPa, about dehydration 2h, when cooling to 40 ℃～50 ℃, add the liquid electrolyte for preparing, after mixing, drip the polyisocyanates that measures, continue to mix, the weight ratio of performed polymer and liquid electrolyte is 1:2～10;
(c) will be in advance 5 * 10
-4MolL
-1Soaked 12 hours nanocrystalline porous TiO in the ethanol solution of bipyridyl ruthenium dye
2Membrane electrode takes out, and dries up, will be modified with again platinum to electrode surface down with TiO
2The electrode alignment is clamped battery with clip; 120 ℃ of lower 15min that place around then sealing with the heat-seal film, are injected into TiO with the above-mentioned electrolyte solution of preparing again in vacuum drying oven
2Between membrane electrode and the platinum electrode, injection is put in battery in the vacuum drying oven after finishing, under (80 ± 10) ℃, insulation 2h, make electrolyte solution generation complete reaction, form the polyurethane gle electrolyte, room temperature to be dropped to namely gets quasi-solid-state dye sensitized solar cell.
5. but the gel electrolyte of the in-situ solidifying for DSSC according to claim 4, it is characterized in that: described bipyridyl ruthenium dye is RuL
2(NCS)
2: 2TBA.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103337365A (en) * | 2013-06-05 | 2013-10-02 | 奇瑞汽车股份有限公司 | A gel electrolyte, a preparation method thereof, and a dye sensitization battery |
| CN104616899A (en) * | 2014-12-19 | 2015-05-13 | 苏州佳亿达电器有限公司 | Method for preparing dye-sensitized solar photovoltaic panel |
| CN106098391A (en) * | 2016-08-04 | 2016-11-09 | 陈毅忠 | A kind of preparation method of quasi solid electrolyte photosensitive fuel |
| KR101819883B1 (en) | 2017-10-26 | 2018-01-19 | 상명대학교 천안산학협력단 | Polymeric gel electrolyte by in-situ cross-linking reaction and electrochemical device including the same |
| CN108417398A (en) * | 2018-04-11 | 2018-08-17 | 北京石油化工学院 | The solid polyelectrolyte of in-situ polymerization and preparation method thereof for dye-sensitized solar cells |
| CN108597883A (en) * | 2018-04-11 | 2018-09-28 | 北京石油化工学院 | A kind of solid electrolyte and preparation method thereof that hardening time is controllable |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002025336A (en) * | 2000-07-10 | 2002-01-25 | Aicello Chemical Co Ltd | Polymer gel electrolyte |
| CN1529922A (en) * | 2001-03-26 | 2004-09-15 | 夏普株式会社 | Dye-sensitized solar cell |
| CN1653558A (en) * | 2002-04-11 | 2005-08-10 | 索尼株式会社 | Solid electrolyte, photoelectric converter and process for producing the same |
-
2012
- 2012-12-28 CN CN201210581131.4A patent/CN103021667B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002025336A (en) * | 2000-07-10 | 2002-01-25 | Aicello Chemical Co Ltd | Polymer gel electrolyte |
| CN1529922A (en) * | 2001-03-26 | 2004-09-15 | 夏普株式会社 | Dye-sensitized solar cell |
| CN1653558A (en) * | 2002-04-11 | 2005-08-10 | 索尼株式会社 | Solid electrolyte, photoelectric converter and process for producing the same |
Non-Patent Citations (1)
| Title |
|---|
| 贾晓辉等: "聚氨酯弹性体的制备", 《化学工程与装备》 * |
Cited By (7)
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| CN103337365A (en) * | 2013-06-05 | 2013-10-02 | 奇瑞汽车股份有限公司 | A gel electrolyte, a preparation method thereof, and a dye sensitization battery |
| CN104616899A (en) * | 2014-12-19 | 2015-05-13 | 苏州佳亿达电器有限公司 | Method for preparing dye-sensitized solar photovoltaic panel |
| CN104616899B (en) * | 2014-12-19 | 2017-09-26 | 苏州佳亿达电器有限公司 | A kind of preparation method of dye sensitization of solar electro-optical package |
| CN106098391A (en) * | 2016-08-04 | 2016-11-09 | 陈毅忠 | A kind of preparation method of quasi solid electrolyte photosensitive fuel |
| KR101819883B1 (en) | 2017-10-26 | 2018-01-19 | 상명대학교 천안산학협력단 | Polymeric gel electrolyte by in-situ cross-linking reaction and electrochemical device including the same |
| CN108417398A (en) * | 2018-04-11 | 2018-08-17 | 北京石油化工学院 | The solid polyelectrolyte of in-situ polymerization and preparation method thereof for dye-sensitized solar cells |
| CN108597883A (en) * | 2018-04-11 | 2018-09-28 | 北京石油化工学院 | A kind of solid electrolyte and preparation method thereof that hardening time is controllable |
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