CN105513800A - Preparation method of low-cost quasi solid electrolyte for dye sensitized solar cell - Google Patents
Preparation method of low-cost quasi solid electrolyte for dye sensitized solar cell Download PDFInfo
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- CN105513800A CN105513800A CN201510997116.1A CN201510997116A CN105513800A CN 105513800 A CN105513800 A CN 105513800A CN 201510997116 A CN201510997116 A CN 201510997116A CN 105513800 A CN105513800 A CN 105513800A
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- hydrogen bond
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- 238000002360 preparation method Methods 0.000 title claims abstract description 63
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 63
- 239000002904 solvent Substances 0.000 claims abstract description 46
- 230000005496 eutectics Effects 0.000 claims abstract description 45
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- 229920000936 Agarose Polymers 0.000 claims abstract description 17
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims abstract description 8
- 235000019743 Choline chloride Nutrition 0.000 claims abstract description 8
- 229960003178 choline chloride Drugs 0.000 claims abstract description 8
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical group [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims abstract description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 7
- JJCWKVUUIFLXNZ-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCO JJCWKVUUIFLXNZ-UHFFFAOYSA-M 0.000 claims abstract description 3
- 206010070834 Sensitisation Diseases 0.000 claims description 42
- 230000008313 sensitization Effects 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 239000007787 solid Substances 0.000 abstract description 13
- 239000003792 electrolyte Substances 0.000 abstract description 12
- 230000005693 optoelectronics Effects 0.000 abstract description 4
- 239000000975 dye Substances 0.000 description 59
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 14
- 238000001291 vacuum drying Methods 0.000 description 13
- 239000002608 ionic liquid Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011521 glass Substances 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 229910010413 TiO 2 Inorganic materials 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000008236 heating water Substances 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 238000010345 tape casting Methods 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- 229910052724 xenon Inorganic materials 0.000 description 7
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 230000013016 learning Effects 0.000 description 5
- 239000011244 liquid electrolyte Substances 0.000 description 4
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical class CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011245 gel electrolyte Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000008272 agar Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 125000003147 glycosyl group Chemical group 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- -1 trifluoromethanesulfonic acid acid amides Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ARSMIBSHEYKMJT-UHFFFAOYSA-M 1,3-dimethylimidazolium iodide Chemical compound [I-].CN1C=C[N+](C)=C1 ARSMIBSHEYKMJT-UHFFFAOYSA-M 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- ZKYGURGLVHDMAB-UHFFFAOYSA-N CN1C=NC=C1.[I] Chemical compound CN1C=NC=C1.[I] ZKYGURGLVHDMAB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/0029—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/0029—Processes of manufacture
- H01G9/0036—Formation of the solid electrolyte layer
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/025—Solid electrolytes
- H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
- H01G9/2013—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte the electrolyte comprising ionic liquids, e.g. alkyl imidazolium iodide
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
- Manufacturing & Machinery (AREA)
Abstract
The invention discloses a preparation method of a low-cost quasi-solid electrolyte for a dye sensitized solar cell. The preparation method includes the following steps that: (1) a deep eutectic solvent is prepared: a hydrogen bond donor and a hydrogen bond acceptor are mixed uniformly and are dried, so that the deep eutectic solvent can be obtained, wherein the hydrogen bond donor is urea or glycerol, and the hydrogen bond acceptor is choline chloride or choline bromide; and (2) the quasi solid state electrolyte is prepared: agarose is added into N-methyl pyrrolidone at first, and an obtained mixture is stirred evenly, and then, I2 and LiI are added into the mixture, and a newly-obtained mixture is stirred evenly, and finally, the deep eutectic solvent is added into the mixture, and the deep eutectic solvent and the mixture are mixed evenly, so that the quasi-solid electrolyte can be obtained. The quasi-solid electrolyte obtained through adopting the preparation method has high ionic conductivity and stability. The deep eutectic solvent adopted by the preparation method of the invention is low in cost and easy to synthetise, and has high ionic conductivity. When the quasi-solid electrolyte is applied to an optoelectronic device, the optoelectronic device can maintain excellent photoelectric performance and high photoelectric conversion efficiency.
Description
Technical field
The invention belongs to field of dye-sensitized solar cells, particularly relate to a kind of low cost, based on the preparation method of the used by dye sensitization solar battery quasi-solid electrolyte of eutectic solvent.
Background technology
DSSC (DSSC) preparation technology is simple, cost is low, in large area industrial applications, have larger advantage, is the solar cell that a class has wide application prospect; Its main composition parts comprise: photosensitizer (dyestuff), electrolyte (containing oxidation-reduction pair), to electrode, electro-conductive glass and titanium dioxide photo anode; Wherein, electrolyte carries the effect of transport charge, is an important component part of DSSC.
Electrolyte mainly comprises: the oxidation-reduction pair (I of good reversibility
-/ I
3-), dissolved oxygen reduction electricity right solvent and additive.Liquid electrolyte, quasi-solid electrolyte and solid electrolyte is divided into by existence.It is high that liquid electrolyte has conductivity, the advantages such as ion diffuse speed is fast, but traditional liquid electrolyte is also due to its extensive use of disadvantages affect (TennakoneK such as its encapsulation are difficult, volatile, poor stability, toxicity are large, PereraVPS, KottegotaIRM, etal.JPhysD:ApplPhys, 1999,, and the diffusion velocity of solid electrolyte intermediate ion is slower 32 (4): 374-379); Conductivity is lower.Thus developing accurate solid gel electrolyte is most effective method.Publication number is that the Chinese patent application of CN103489645A discloses a kind of used by dye sensitization solar battery gel electrolyte and preparation method thereof, by functional form Graphene, ionomer
ionic liquid
tert .-butylpyridine and two trifluoromethanesulfonic acid acid amides are mixed with by a certain percentage, and gained electrolyte gel ability is strong, and be easy to encapsulation, prepared dye-sensitized cell also has high electricity conversion.But the ionic liquid that the method adopts synthesis difficulty, cost are higher.Publication number is that the Chinese patent application of CN101635200A discloses a kind of dye-sensitized solar cell electrolyte and preparation method thereof: by non-polymeric ionic liquid
aggretion type ionic liquid (
in one), ionic liquid crosslinking agent
with initator (benzoin ethyl ether,
in one) mix after prepare Quasi-solid-state polymer gel electrolyte by in-situ polymerization, the electrolyte prepared by the method has good adhesive property, be easy to encapsulation; But use the photoelectric conversion efficiency of this electrolytical battery to need to improve further, preparation method is also comparatively complicated.
As known from the above, ionic liquid (imidazoles, sulfonium class, pyridines and guanidine salt) is a conventional part of quasi-solid electrolyte, play the great function increasing cell photoelectric performance, but because the synthesis mode of its complexity and high cost limit ionic liquid application in the opto-electronic device, as conventional 1,3-methylimidazole salt compounded of iodine (CAS 4333-62-4) in lark prestige official website product inexpensively still price be.Therefore, quasi solid electrolyte that research and develop a kind of low cost, that be easy to synthesis, and this electrolytical cell photoelectric conversion efficiency of use can be improved again, be necessary.
Summary of the invention
The technical problem to be solved in the present invention overcomes the deficiencies in the prior art, provides a kind of and be easy to preparation method that synthesize, low cost used by dye sensitization solar battery quasi-solid electrolyte.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is:
A preparation method for low cost used by dye sensitization solar battery quasi-solid electrolyte, comprises the following steps:
(1) prepare eutectic solvent: hydrogen bond donor and hydrogen bond receptor to be mixed, dry, obtain eutectic solvent; Described hydrogen bond donor is urea (CO (NH
2)
2) or glycerine (C
3h
80
3), described hydrogen bond receptor is Choline Chloride (HOCH
2cH
2n (CH
3)
3or choline bromide (HOCH Cl)
2cH
2n (CH
3)
3cl);
(2) quasi-solid electrolyte is prepared: first add after agarose stirs in 1-METHYLPYRROLIDONE (NMP), then add I
2continue to stir with LiI, finally add eutectic solvent prepared by step (1) and mix and namely obtain described quasi-solid electrolyte.
Above-mentioned preparation method, preferably, the mol ratio of described hydrogen bond donor and described hydrogen bond receptor is 2 ~ 2.5:1.Described hydrogen bond donor and described hydrogen bond receptor all pass through abundant drying and dehydrating.
Above-mentioned preparation method, preferably, in described step (2), the mass fraction that the addition of eutectic solvent accounts for quasi-solid electrolyte is 10wt.% ~ 80wt.%.
Above-mentioned preparation method, preferably, the addition of described agarose is the 2wt.% ~ 3.5wt.% of 1-METHYLPYRROLIDONE; Described I
2addition be the 1.2wt.% ~ 1.4wt.% of 1-METHYLPYRROLIDONE; LiI and I
2mol ratio be 1 ~ 1.5:1.
Above-mentioned preparation method, preferably, in described step (1), the concrete preparation process of eutectic solvent is: under 80 ~ 90 DEG C of water-baths, stir 2 ~ 2.5h by after hydrogen bond donor and hydrogen bond receptor mixing, obtain water white liquid then by this water white liquid vacuum drying 16 ~ 24h, namely obtain eutectic solvent.
Above-mentioned preparation method, preferably, in described step (2), the concrete preparation process of quasi-solid electrolyte is: in 1-METHYLPYRROLIDONE, add agarose, stops water-bath, then add I after 4 ~ 4.5h is stirred in 80 ~ 90 DEG C of waters bath with thermostatic control
2and LiI, stir 4 ~ 5h to evenly, finally add eutectic solvent, continuing stirring 4 ~ 4.5h to mixing, namely obtaining electrolyte.Further, I
2, LiI and agarose all adopt analyze pure.
Applicant is found by research, the eutectic solvent that hydrogen bond receptor and hydrogen bond donor are formed equally also is a kind of ionic liquid, by research, applicant also finds that the eutectic solvent that hydrogen bond receptor and hydrogen bond donor are mixed to form is had low-steam pressure, broadening window, the advantage such as high thermal stability and high conductivity, this eutectic solvent is compared to other kind ionic liquids simultaneously, also there is synthesis simple, be easy to reclaim, the advantage such as with low cost, the eutectic solvent synthesis presoma price display urea provided by lark prestige official website is $141/kg, Lv Huadanjian $2.4/g, well below the price of other ionic liquids.This type of eutectic solvent ionic liquid is replaced the ionic liquid of expensive traditional and is successfully applied to photoelectric device by applicant, greatly reduces the cost of photoelectric device.
The present invention by adding appropriate eutectic solvent (hydrogen bond receptor and hydrogen bond donor) in agarose base polymer electrolyte, hydrogen bond donor, hydrogen bond receptor directly and agarose interact, increase the network cross-linked structure of electrolyte system, for the transmission of electrolyte intermediate ion provides effective carrier transport passage, finally reach and improve electrolytical ionic conductivity, strengthen the object of the photoelectric properties of solar device.
Compared with prior art, the invention has the advantages that:
The electrolyte that preparation method of the present invention makes is as the criterion solid-state, has larger ionic conductivity and stability; Quasi-solid electrolyte is attached on device after being polymerized to electrolyte and becomes solid film, therefore there is not leakage problems in use procedure; Compared to liquid electrolyte, the eutectic solvent cost introduced in preparation method's process of the present invention is lower, is easy to synthesis, has higher ionic conductivity, and application makes optics keep higher photoelectric properties and photoelectric conversion efficiency in the opto-electronic device.
Embodiment
For the ease of understanding the present invention, hereafter will do to describe more comprehensively, meticulously to the present invention in conjunction with preferred embodiment, but protection scope of the present invention is not limited to following specific embodiment.
Unless otherwise defined, hereinafter used all technical terms are identical with the implication that those skilled in the art understand usually.The object of technical term used herein just in order to describe specific embodiment is not be intended to limit the scope of the invention.
Apart from special instruction, the various reagent used in the present invention, raw material are can commodity commercially or can by the obtained product of known method.
Embodiment 1:
A preparation method for low cost used by dye sensitization solar battery quasi-solid electrolyte of the present invention, comprises the following steps:
(1) preparation of eutectic solvent: room temperature calls the 12.000g solid urea of the abundant drying and dehydrating of learning from else's experience in the following text and 13.950g solid choline chloride puts into brown bottle, is placed in 80 DEG C of water-baths and adds thermal agitation 2h, until be converted into colourless transparent liquid completely.Take out, be statically placed in vacuum drying chamber and take out after dry 16h, be eutectic solvent.
(2) electrolytical preparation: get 20.45gNMP, puts into 60mL brown bottle, adds 0.4301g agarose, after stirring 4h, takes out brown bottle, adds 0.2782gI under the condition of 80 DEG C of heating water baths
2with 0.1261gLiI, stirred at ambient temperature 4.3h, after having stirred, gets eutectic solvent prepared by 2.62g step (1), adds in brown bottle, continues to stir 4h, obtain quasi-solid electrolyte under room temperature.
(3) preparation of light anode and sensitization: adopt knife coating procedure by TiO
2slip (solid-liquid mass ratio 1:7) is coated on conductive glass surface, makes it film forming, after 35 minutes through 500 DEG C of heat treatments, puts into and be dissolved with 0.4 × 10
-3in the ethanol solution of mol/LN719 dyestuff, at room temperature sensitization 12h, obtains the TiO of dye sensitization
2light anode.
(4) preparation of battery device: quasi-solid electrolyte step (2) prepared drips the TiO of the dye sensitization prepared in step (3)
2on light anode, put into vacuum drying chamber, be warming up to 80 DEG C, insulation 1h, makes quasi-solid electrolyte be contracted to thick, adds electrode, continue to toast 1h at 85 DEG C, make quasi-solid-state dye sensitized solar cell.
The performance of gained quasi-solid electrolyte in test the present embodiment step (2): under room temperature environment, employing platinum electrode is test electrode, and recording electrolytical conductivity is 4.32 × 10
-3s/cm.
The performance of the quasi-solid-state dye sensitized solar cell of test the present embodiment gained: in room temperature environment, use xenon lamp simulated solar irradiation, light intensity is 80mW/cm
2(light intensity: under using silicon photoelectric diode demarcation condition), record quasi-solid-state dye sensitized solar cell, effective illuminating area is 0.25cm
2photoelectric conversion efficiency be 1.73%.
Embodiment 2:
A preparation method for low cost used by dye sensitization solar battery quasi-solid electrolyte of the present invention, comprises the following steps:
(1) preparation of eutectic solvent: room temperature is called the solid urea 12.000g of the abundant drying and dehydrating of learning from else's experience and solid choline chloride 13.530g in the following text and put into brown bottle, be placed in 82 DEG C of water-baths and add thermal agitation 2.2h, until be converted into colourless transparent liquid completely.Take out, be statically placed in vacuum drying chamber and take out after dry 18h, be eutectic solvent.
(2) electrolytical preparation: get 20.45gNMP and put into 60mL brown bottle, add 0.5153g agarose, after stirring 4.2h, takes out brown bottle, adds 0.2563gI under the condition of 82 DEG C of heating water baths
2with 0.1231gLiI, stirred at ambient temperature 4.7h, after having stirred, gets eutectic solvent prepared by 4.11g step (1), adds in brown bottle, continues to stir 4.2h, obtain quasi-solid electrolyte under room temperature.
(3) preparation of light anode and sensitization: adopt knife coating procedure by TiO
2slip (solid-liquid mass ratio 1:7) is coated on conductive glass surface, makes it film forming, after 35 minutes, puts into 0.4 × 10 through 500 DEG C of heat treatments
-3in the N719 dyestuff ethanol solution of mol/L, at room temperature sensitization 12h, obtains the TiO of dye sensitization
2light anode.
(4) preparation of battery device: quasi-solid electrolyte step (2) prepared drips the TiO of the dye sensitization prepared in step (3)
2on light anode, put into vacuum drying chamber, be warming up to 80 DEG C, insulation 1h, makes quasi-solid electrolyte be contracted to thick, adds electrode, continue to toast 1h at 85 DEG C, make quasi-solid-state dye sensitized solar cell.
The performance of gained quasi-solid electrolyte in test the present embodiment step (2): under room temperature environment, employing platinum electrode is test electrode, and recording electrolytical conductivity is 7.36 × 10
-3s/cm.
The performance of the quasi-solid-state dye sensitized solar cell of test the present embodiment gained: in room temperature environment, use xenon lamp simulated solar irradiation, light intensity is 80mW/cm
2(light intensity: under using silicon photoelectric diode demarcation condition), record quasi-solid-state dye sensitized solar cell, effective illuminating area is 0.25cm
2photoelectric conversion efficiency be 2.81%.
Embodiment 3:
A preparation method for low cost used by dye sensitization solar battery quasi-solid electrolyte of the present invention, comprises the following steps:
(1) preparation of eutectic solvent: room temperature is called the solid urea 12.000g of the abundant drying and dehydrating of learning from else's experience and solid choline chloride 13.000g in the following text and put into brown bottle, be placed in 84 DEG C of water-baths and add thermal agitation 2.4h, until be converted into colourless transparent liquid completely.Take out, be statically placed in vacuum drying chamber and take out after dry 20h, be eutectic solvent.
(2) electrolytical preparation: get 20.45gNMP and put into 60mL brown bottle, add 0.6045g agarose, after stirring 4.3h, takes out brown bottle, adds 0.2802gI under the condition of 85 DEG C of heating water baths
2with 0.1398gLiI, stirred at ambient temperature 5h, after having stirred, gets eutectic solvent prepared by 12.27g step (1), adds in brown bottle, continues to stir 4.4h, obtain quasi-solid electrolyte under room temperature.
(3) preparation of light anode and sensitization: adopt knife coating procedure by TiO
2slip (solid-liquid mass ratio 1:7) is coated on conductive glass surface, makes it film forming, after 35 minutes, puts into 0.4 × 10 through 500 DEG C of heat treatments
-3in the N719 dyestuff ethanol solution of mol/L, at room temperature sensitization 12h, obtains the TiO of dye sensitization
2light anode.
(4) preparation of battery device: quasi-solid electrolyte step (2) prepared drips the TiO of the dye sensitization prepared in step (3)
2on light anode, put into vacuum drying chamber, be warming up to 80 DEG C, insulation 1h, makes quasi-solid electrolyte be contracted to thick, adds electrode, continue to toast 1h at 85 DEG C, make quasi-solid-state dye sensitized solar cell.
The performance of gained quasi-solid electrolyte in test the present embodiment step (2): under room temperature environment, employing platinum electrode is test electrode, and recording electrolytical conductivity is 5.11 × 10
-3s/cm.
The performance of the quasi-solid-state dye sensitized solar cell of test the present embodiment gained: in room temperature environment, use xenon lamp simulated solar irradiation, light intensity is 80mW/cm
2(light intensity: under using silicon photoelectric diode demarcation condition), record quasi-solid-state dye sensitized solar cell, effective illuminating area is 0.25cm
2photoelectric conversion efficiency be 2.01%.
Embodiment 4:
A preparation method for low cost used by dye sensitization solar battery quasi-solid electrolyte of the present invention, comprises the following steps:
(1) preparation of eutectic solvent: room temperature is called the solid urea 12.000g of the abundant drying and dehydrating of learning from else's experience and solid choline chloride 12.982g in the following text and put into brown bottle, be placed in 87 DEG C of water-baths and add thermal agitation 2.5h, until be converted into colourless transparent liquid completely.Take out, be statically placed in vacuum drying chamber and take out after dry 21h, be eutectic solvent.
(2) electrolytical preparation: get 20.45gNMP and put into 60mL brown bottle, add 0.7011g agarose, after stirring 4.4h, takes out brown bottle, adds 0.2852gI under the condition of 87 DEG C of heating water baths
2with 0.1413gLiI, stirred at ambient temperature 5h, after having stirred, gets eutectic solvent prepared by 16.15g step (1), adds in brown bottle, continues to stir 4.5h, obtain quasi-solid electrolyte under room temperature.
(3) preparation of light anode and sensitization: adopt knife coating procedure by TiO
2slip (solid-liquid mass ratio 1:7) is coated on conductive glass surface, makes it film forming, after 35 minutes, puts into 0.4 × 10 through 500 DEG C of heat treatments
-3in the N719 dyestuff ethanol solution of mol/L, at room temperature sensitization 12h, obtains the TiO of dye sensitization
2light anode.
(4) preparation of battery device: quasi-solid electrolyte step (2) prepared drips the TiO of the dye sensitization prepared in step (3)
2on light anode, put into vacuum drying chamber, be warming up to 80 DEG C, insulation 1h, makes quasi-solid electrolyte be contracted to thick, adds electrode, continue to toast 1h at 85 DEG C, make quasi-solid-state dye sensitized solar cell.
The performance of gained quasi-solid electrolyte in test the present embodiment step (2): under room temperature environment, employing platinum electrode is test electrode, and recording electrolytical conductivity is 4.35 × 10
-3s/cm.
The performance of the quasi-solid-state dye sensitized solar cell of test the present embodiment gained: in room temperature environment, use xenon lamp simulated solar irradiation, light intensity is 80mW/cm
2(light intensity: under using silicon photoelectric diode demarcation condition), record quasi-solid-state dye sensitized solar cell, effective illuminating area is 0.25cm
2photoelectric conversion efficiency be 1.55%.
Embodiment 5:
A preparation method for low cost used by dye sensitization solar battery quasi-solid electrolyte of the present invention, comprises the following steps:
(1) preparation of eutectic solvent: room temperature is called the solid urea 12.000g of the abundant drying and dehydrating of learning from else's experience and solid choline chloride 12.523g in the following text and put into brown bottle, be placed in 90 DEG C of water-baths and add thermal agitation 2.2h, until be converted into colourless transparent liquid completely.Take out, be statically placed in vacuum drying chamber and take out after dry 24h, be eutectic solvent.
(2) electrolytical preparation: get 20.45gNMP and put into 60mL brown bottle, add 0.5153g agarose, after stirring 4.5h, takes out brown bottle, adds 0.2563gI under the condition of 90 DEG C of heating water baths
2with 0.1231gLiI, stirred at ambient temperature 4.7h, after having stirred, gets eutectic solvent prepared by 4.11g step (1), adds in brown bottle, continues to stir 4.2h, obtain quasi-solid electrolyte under room temperature.
(3) preparation of light anode and sensitization: adopt knife coating procedure by TiO
2slip (solid-liquid mass ratio 1:7) is coated on conductive glass surface, makes it film forming, after 35 minutes, puts into 0.4 × 10 through 500 DEG C of heat treatments
-3in the N719 dyestuff ethanol solution of mol/L, at room temperature sensitization 12h, obtains the TiO of dye sensitization
2light anode.
(4) preparation of battery device: quasi-solid electrolyte step (2) prepared drips the TiO of the dye sensitization prepared in step (3)
2on light anode, put into vacuum drying chamber, be warming up to 80 DEG C, insulation 1h, makes quasi-solid electrolyte be contracted to thick, adds electrode, continue to toast 1h at 85 DEG C, make quasi-solid-state dye sensitized solar cell.
The performance of gained quasi-solid electrolyte in test the present embodiment step (2): under room temperature environment, employing platinum electrode is test electrode, and recording electrolytical conductivity is 4.36 × 10
-3s/cm.
The performance of the quasi-solid-state dye sensitized solar cell of test the present embodiment gained: in room temperature environment, use xenon lamp simulated solar irradiation, light intensity is 80mW/cm
2(light intensity: under using silicon photoelectric diode demarcation condition), record quasi-solid-state dye sensitized solar cell, effective illuminating area is 0.25cm
2photoelectric conversion efficiency be 1.66%.
Comparative example 1:
The preparation method of the used by dye sensitization solar battery quasi-solid electrolyte of this comparative example, comprises the following steps:
(1) electrolytical preparation: get 20.25gNMP and put into 60mL brown bottle, add 0.4133g agarose, after stirring 4h, takes out brown bottle, adds 0.2982gI under the condition of 80 DEG C of heating water baths
2with 0.1261gLiI, stirred at ambient temperature 4h, then add 1,3-methylimidazole iodine, obtain the quasi-solid electrolyte of agar glycosyl.
(2) preparation of light anode and sensitization: adopt knife coating procedure by TiO
2slip (solid-liquid mass ratio 1:7) is coated on conductive glass surface, makes it film forming, after 35 minutes, puts into 0.4 × 10 through 500 DEG C of heat treatments
-3in the N719 dyestuff ethanol solution of mol/L, at room temperature sensitization 12h, obtains the TiO of dye sensitization
2light anode.
(3) preparation of battery device: quasi-solid electrolyte step (1) prepared drips the TiO of the dye sensitization prepared in step (2)
2on light anode, put into vacuum drying chamber, be warming up to 80 DEG C, insulation 1h, makes quasi-solid electrolyte be contracted to thick, adds electrode, continue to toast 1h at 85 DEG C, make quasi-solid-state dye sensitized solar cell.
Test the performance of gained quasi-solid electrolyte in this comparative example step (1): under room temperature environment, employing platinum electrode is test electrode, and recording electrolytical conductivity is 2.89 × 10
-3s/cm.
Test the performance of the quasi-solid-state dye sensitized solar cell of this comparative example gained: in room temperature environment, use xenon lamp simulated solar irradiation, light intensity is 80mW/cm
2(light intensity: under using silicon photoelectric diode demarcation condition), record quasi-solid-state dye sensitized solar cell, effective illuminating area is 0.25cm
2photoelectric conversion efficiency be 1.25%.
From comparative example 1 and embodiment 1-5, through the interpolation of eutectic solvent, make the photoelectric efficiency of quasi-solid-state dye sensitized solar cell at least be increased to 1.55% by 1.25%, conductivity is also by 2.89 × 10
-3s/cm is at least elevated to 4.32 × 10
-3s/cm.When mass fraction shared by eutectic solvent is 20wt.%, obtains ideal electrolytic conductivity and photoelectric efficiency, be respectively 7.36 × 10
-3s/cm and 2.81%.
Comparative example 2:
The preparation method of the used by dye sensitization solar battery quasi-solid electrolyte of this comparative example, comprises the following steps:
(1) electrolytical preparation: get 20.25gNMP and put into 60mL brown bottle, add 0.4133g agarose, after stirring 4h, takes out brown bottle, adds 0.2982gI under the condition of 80 DEG C of heating water baths
2with 0.1261gLiI, stirred at ambient temperature 4h, adds 1, the 3-methylimidazole iodine that mass fraction is 20wt.%, obtains the quasi-solid electrolyte of agar glycosyl.
(2) preparation of light anode and sensitization: adopt knife coating procedure by TiO
2slip (solid-liquid mass ratio 1:7) is coated on conductive glass surface, makes it film forming, after 35 minutes, puts into 0.4 × 10 through 500 DEG C of heat treatments
-3in the N719 dyestuff ethanol solution of mol/L, at room temperature sensitization 12h, obtains the TiO of dye sensitization
2light anode.
(3) preparation of battery device: quasi-solid electrolyte step (1) prepared drips the TiO of the dye sensitization prepared in step (2)
2on light anode, put into vacuum drying chamber, be warming up to 80 DEG C, insulation 1h, makes quasi-solid electrolyte be contracted to thick, adds electrode, continue to toast 1h at 85 DEG C, make quasi-solid-state dye sensitized solar cell.
Test the performance of gained quasi-solid electrolyte in this comparative example step (1): under room temperature environment, employing platinum electrode is test electrode, and recording electrolytical conductivity is 3.21 × 10
-3s/cm.
Test the performance of the quasi-solid-state dye sensitized solar cell of this comparative example gained: in room temperature environment, use xenon lamp simulated solar irradiation, light intensity is 80mW/cm
2(light intensity: under using silicon photoelectric diode demarcation condition), record quasi-solid-state dye sensitized solar cell, effective illuminating area is 0.25cm
2photoelectric conversion efficiency be 1.47%.
From comparative example 2 compared with embodiment 1-5, if eutectic solvent to be replaced by price 1,3-methylimidazole iodine costly, the photoelectric efficiency of gained DSSC is only 1.47%, and electrolytic conductivity is 3.21 × 10
-3s/cm, and electrolytic conductivity of the present invention at least also reaches 4.35 × 10
-3s/cm, cell photoelectric efficiency is 1.55% (embodiment 5), and even, electrolytical conductivity of the present invention can reach 7.36 × 10
-3s/cm, photoelectric conversion efficiency can reach 2.81% (see embodiment 2).Thus, quasi-solid electrolyte of the present invention not only cost is low, and synthetic method is simple, adopts the photoelectric properties of the DSSC of this quasi-solid electrolyte to be also greatly improved.
To sum up, the synthetic method of used by dye sensitization solar battery quasi-solid electrolyte of the present invention is simple, and raw material sources are extensive, with low cost.Use the quasi-solid-state dye sensitized solar cell prepared by this method, electrolytical conductivity and permeability all improve, and finally improve the photoelectric efficiency of quasi-solid-state dye sensitized solar cell.
Claims (6)
1. a preparation method for low cost used by dye sensitization solar battery quasi-solid electrolyte, is characterized in that, comprises the following steps:
(1) prepare eutectic solvent: hydrogen bond donor and hydrogen bond receptor to be mixed, dry, obtain eutectic solvent; Described hydrogen bond donor is urea or glycerine, and described hydrogen bond receptor is Choline Chloride or choline bromide;
(2) quasi-solid electrolyte is prepared: first add after agarose stirs in 1-METHYLPYRROLIDONE, then add I
2continue to stir with LiI, finally add eutectic solvent prepared by step (1) and mix and namely obtain described quasi-solid electrolyte.
2. preparation method as claimed in claim 1, it is characterized in that, the mol ratio of described hydrogen bond donor and described hydrogen bond receptor is 2 ~ 2.5:1.
3. preparation method as claimed in claim 1, is characterized in that, in described step (2), the mass fraction that the addition of eutectic solvent accounts for quasi-solid electrolyte is 10wt.% ~ 80wt.%.
4. preparation method as claimed in claim 1, it is characterized in that, the addition of described agarose is the 2wt.% ~ 3.5wt.% of 1-METHYLPYRROLIDONE; Described I
2addition be the 1.2wt.% ~ 1.4wt.% of 1-METHYLPYRROLIDONE; LiI and I
2mol ratio be 1 ~ 1.5:1.
5. preparation method as claimed in claim 1, it is characterized in that, in described step (1), the concrete preparation process of eutectic solvent is: under 80 ~ 90 DEG C of water-baths, stir 2 ~ 2.5h by after hydrogen bond donor and hydrogen bond receptor mixing, then vacuumize 16 ~ 24h, namely obtains eutectic solvent.
6. preparation method as claimed in claim 1, it is characterized in that, in described step (2), the concrete preparation process of quasi-solid electrolyte is: in 1-METHYLPYRROLIDONE, add agarose, stop water-bath after 4 ~ 4.5h is stirred in 80 ~ 90 DEG C of waters bath with thermostatic control, then add I
2and LiI, stir 4 ~ 5h to evenly, finally add eutectic solvent, continuing stirring 4 ~ 4.5h to mixing, namely obtaining quasi-solid electrolyte.
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| CN106653374A (en) * | 2016-11-18 | 2017-05-10 | 中南大学 | Polymer electrolyte for dye-sensitized solar cell and preparation method of polymer electrolyte |
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| CN110010966A (en) * | 2019-04-15 | 2019-07-12 | 哈尔滨理工大学 | A kind of biopolymer electrolyte preparation method taken water as a solvent |
| CN110218338A (en) * | 2019-05-21 | 2019-09-10 | 江汉大学 | A kind of conduction gelatin method for producing elastomers |
| CN111675239A (en) * | 2020-04-28 | 2020-09-18 | 廊坊师范学院 | Method for dissolving and extracting lead iodide by using polyethylene glycol type eutectic solvent |
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|---|---|---|---|---|
| CN106653374A (en) * | 2016-11-18 | 2017-05-10 | 中南大学 | Polymer electrolyte for dye-sensitized solar cell and preparation method of polymer electrolyte |
| CN106653374B (en) * | 2016-11-18 | 2019-03-05 | 中南大学 | Used by dye sensitization solar battery polymer dielectric and preparation method thereof |
| CN109119692A (en) * | 2018-09-26 | 2019-01-01 | 烟台大学 | A kind of electrolyte adding deep congruent melting agent and the low temperature resistant lithium-sulfur cell comprising the electrolyte |
| CN110010966A (en) * | 2019-04-15 | 2019-07-12 | 哈尔滨理工大学 | A kind of biopolymer electrolyte preparation method taken water as a solvent |
| CN110218338A (en) * | 2019-05-21 | 2019-09-10 | 江汉大学 | A kind of conduction gelatin method for producing elastomers |
| CN111675239A (en) * | 2020-04-28 | 2020-09-18 | 廊坊师范学院 | Method for dissolving and extracting lead iodide by using polyethylene glycol type eutectic solvent |
| CN111675239B (en) * | 2020-04-28 | 2022-07-08 | 廊坊师范学院 | Method for dissolving and extracting lead iodide by using polyethylene glycol type eutectic solvent |
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