CN106653374A - Polymer electrolyte for dye-sensitized solar cell and preparation method of polymer electrolyte - Google Patents
Polymer electrolyte for dye-sensitized solar cell and preparation method of polymer electrolyte Download PDFInfo
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- CN106653374A CN106653374A CN201611016530.0A CN201611016530A CN106653374A CN 106653374 A CN106653374 A CN 106653374A CN 201611016530 A CN201611016530 A CN 201611016530A CN 106653374 A CN106653374 A CN 106653374A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 39
- 229920000936 Agarose Polymers 0.000 claims abstract description 24
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 15
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011630 iodine Substances 0.000 claims abstract description 15
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229920000642 polymer Polymers 0.000 claims description 70
- 206010070834 Sensitisation Diseases 0.000 claims description 50
- 230000008313 sensitization Effects 0.000 claims description 50
- 238000003756 stirring Methods 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 6
- 235000009518 sodium iodide Nutrition 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 36
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000012456 homogeneous solution Substances 0.000 abstract 4
- 150000002496 iodine Chemical class 0.000 abstract 2
- 239000000975 dye Substances 0.000 description 55
- 238000012360 testing method Methods 0.000 description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 230000009466 transformation Effects 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 229910052697 platinum Inorganic materials 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000008236 heating water Substances 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
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000009396 hybridization Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000007784 solid electrolyte Substances 0.000 description 5
- 230000033116 oxidation-reduction process Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000011245 gel electrolyte Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920001817 Agar Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000008272 agar Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910003119 ZnCo2O4 Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000003147 glycosyl group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920003228 poly(4-vinyl pyridine) Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 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
- H01G9/20—Light-sensitive devices
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
- H01G9/2009—Solid electrolytes
-
- 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
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Hybrid Cells (AREA)
- Materials Engineering (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention discloses a polymer electrolyte for a dye-sensitized solar cell. An organic-inorganic hybrid two-dimensional material is added to the polymer electrolyte; the organic-inorganic hybrid two-dimensional material is made of one or more materials selected from two kinds of substances which are presented by molecular formulas described in the descriptions of the invention. The preparation method of the polymer electrolyte includes the following steps that: agarose is added into to N-Methyl pyrrolidone, and the agarose and the N-Methyl pyrrolidone are stirred evenly at the constant temperature of water bath, so that a homogeneous solution can be formed; after the homogeneous solution is cooled, iodine and iodine salt are added into the homogeneous solution at room temperature, and the iodine, the iodine salt and the homogeneous solution are stirred evenly; and the organic-inorganic hybrid two-dimensional material is added into an obtained solution, and the solution is stirred until the organic-inorganic hybrid two-dimensional material is completely dissolved, namely, the preparation of the polymer electrolyte is completed. The polymer electrolyte for the dye-sensitized solar cell of the invention has great stability; the organic-inorganic hybrid two-dimensional material is added into the polymer electrolyte, and therefore, an additional charge channel is provided, and the electrical conductivity of the electrolyte is improved.
Description
Technical field
The invention belongs to field of dye-sensitized solar cells, more particularly to it is a kind of based on hybrid inorganic-organic two dimension material
Material polymer dielectric and preparation method thereof.
Background technology
DSSC (DSSC) have relatively low production cost, be easy to industrialized production technology and
Wide prospect of production, has attracted the vast concern of business people.DSSC main composition parts include：Titanium dioxide photo anode
Perforated membrane, photosensitizer (dyestuff), electrolyte (contain oxidation-reduction pair), to electrode (platinum is to electrode, polyaniline to electrode etc.)；
Wherein, being in the nature for electrolyte is capable of conductive solution, carries the task of transport charge.
Electrolyte is according to the be divided into liquid electrolyte of existence, quasi-solid electrolyte and solid electrolyte.Traditional liquid
State electrolyte has relatively low viscosity, the transfer rate of oxidation-reduction pair faster, is the most commonly used electrolyte, but should
Kind of electrolyte solvent is volatile, may with sealant reaction, toxicity is big the problems such as affect its stability with following application.And solid-state
Electrolyte has good long-time stability, but electrolyte intermediate ion diffusion velocity is slow and electrical conductivity is low, affects its application.It is accurate
Solid electrolyte is including polymer dielectric, high molecular polymer, nano-particle between liquid and solid electrolyte
Deng, wherein polymer dielectric has a high relative molecular mass, stable space structure framework and good mechanical strength, but
This electrolytelike electric conductivity is poor, and electrolyte and light anode and, such shortcoming limit higher to the impedance between electrode interface
The application of polymer dielectric is made.
The gel electrolyte that the A of China Patent Publication No. CN 103489645 is proposed is by graphene oxideIntroduce ionomer Ionic liquidIn, due to the introducing of graphene oxide, institute
The higher ionic conductivity of electrolyte is prepared, without toxic reagent, but this kind of electrolyte ingredient complexity, desired ion class of liquids
More, Material synthesis are difficult, and preparation cost is high.The polymer gel electricity that the A of China Patent Publication No. CN 101483104 is proposed
Solution matter and preparation method thereof, using polyethylene glycol or polypropylene glycol as polymeric system, adds silane coupler (positive silicic acid second
Ester/methyl silicate/butyl silicate) and inorganic sol particle (silica) as modifying agent, obtain polymer dielectric,
Polymer dielectric prepared by the method has a good heat endurance, and preparation method is simple, but the electrolyte preparation cost compared with
Height, and electrical conductivity is low, limits the application of the electrolyte.The dyestuff that the A of China Patent Publication No. CN 103489644 is proposed is quick
Change polymer iodide gel electrolyte used for solar batteries and preparation method thereof, prepared gel electrolyte is miscellaneous with N- by side chain
The polymer (PVP, P4VP) of ring, elemental iodine, organic solvent (PC, EC) and PVDF are constituted, polymer gel prepared by the method
Electrolysis complicated component, prepares difficulty, and stability is poor, it is difficult to apply.
Analyze from more than, current used by dye sensitization solar battery polymer dielectric needs species numerous mostly
Many chemicals and the synthesis step of complexity, and electrical conductivity is low.Therefore, research and develop a kind of environmental protection, stablize, while high electricity
Lead, the quasi-solid electrolyte of simple structure, the photoelectric efficiency of DSSC can be increased substantially.
The content of the invention
The technical problem to be solved is to overcome the shortcomings of to be mentioned and defect in background above technology, there is provided one
Used by dye sensitization solar battery is planted based on hybrid inorganic-organic two-dimensional material polymer dielectric and preparation method thereof.
To solve above-mentioned technical problem, technical scheme proposed by the present invention is：
A kind of used by dye sensitization solar battery polymer dielectric, is added with organic-nothing in the polymer dielectric
Machine hydridization two-dimensional material, the hybrid inorganic-organic two-dimensional material is selected fromIn one kind
Or it is several.
Used as a total inventive concept, the present invention also provides a kind of above-mentioned method for preparing polymer electrolytes, wraps
Include following steps：
(1) agarose is added in 1-METHYLPYRROLIDONE, is stirred under the conditions of constant temperature water bath, form uniform solution；
(2) after uniform solution cooling prepared by step (1), iodine and salt compounded of iodine is added to continue to stir equal at normal temperatures
It is even；
(3) hybrid inorganic-organic two-dimensional material is added, stirs to it and be completely dissolved, that is, complete the polymer dielectric
Preparation.
Above-mentioned preparation method, it is preferred that the structure of the agarose is：
Above-mentioned preparation method, it is preferred that the addition of the agarose is the 3wt.% of 1-METHYLPYRROLIDONE quality
～4.5wt.%.Applicant by substantial amounts of experimental studies have found that, agar sugared content is too low, it is impossible to form polymer backbone, structure
Into quasi- solid state solar cell；During agarose too high levels, substantial amounts of polymer can be formed and reunited, hinder the ion in electrolyte
Transmission, lowers ionic conductivity.
Above-mentioned preparation method, it is preferred that the salt compounded of iodine is selected from one or more of lithium iodide, sodium iodide.
Above-mentioned preparation method, it is preferred that the addition of the iodine is 1-METHYLPYRROLIDONE quality
0.12wt.%～0.15wt.%；The salt compounded of iodine is 1～1.5 with the molar ratio of iodine.Iodine in the electrolyte can be with
I-Form oxidation-reduction pair I-/I3 -, wherein I-Ground state is reduced in light anode, and I3 -To anodizing into I-, iodine contains
Amount is too high or too low, can cause oxidation-reduction pair I-/I3 -Composition is unbalanced, and electrolyte intermediate ion is transmitted by larger shadow
Ring.
Above-mentioned preparation method, it is preferred that the addition of the hybrid inorganic-organic two-dimensional material is agarose
2wt.%～4wt.%.When the addition of hybrid inorganic-organic two-dimensional material of the present invention is too low, it is impossible to play modifying function；And
When addition is excessive, due to the effect of organic group in hybrid inorganic-organic two-dimensional material, the skeleton knot of polymer can be destroyed
Structure, reduces electron propagation ducts.
Above-mentioned preparation method, it is preferred that in the step (1), bath temperature is 70～90 DEG C, and mixing speed is 500
～700r/min, mixing time is 3.5～5h.
Above-mentioned preparation method, it is preferred that in the step (2), mixing speed be 500～700r/min, stirring when
Between be 3.5～5h.
Above-mentioned preparation method, it is preferred that in the step (3), mixing speed be 500～700r/min, stirring when
Between be 4～6h.
The introducing hybrid inorganic-organic two in used by dye sensitization solar battery polymer dielectric of novelty of the present invention
Dimension material, the hybrid inorganic-organic two-dimensional materialWith higher conductance, compared to graphite
The two-dimensional materials such as alkene, molybdenum sulfide, the C-O bases in its organic structure, it will the hydroxyl between agarose interacts, increase polymerization
The network cross-linked structure of thing electrolyte so as to good dissolubility energy and dispersive property, and extra electron channel is provided；
In addition, applicant also has found that the hybrid inorganic-organic two-dimensional material is for I by research3 -/I-With catalytic action, promote electricity
Son transfer；Applicant is introduced into such two-dimensional material in polymer dielectric, and is successfully applied to DSSC,
The electrical conductivity of electrolyte is substantially increased, the ionic conductivity for improving electrolyte is finally reached, the light of solar device is enhanced
Electrical property.
Compared with prior art, it is an advantage of the current invention that：
(1) used by dye sensitization solar battery polymer dielectric of the invention, with larger stability；The polymer
Hybrid inorganic-organic two-dimensional material is introduced in electrolyte, there is provided additional charge passage, improve the electrical conductivity of electrolyte.
(2) polymer dielectric of the invention is polymerized to be attached to into solid film on device after electrolyte, therefore uses
During there are no leakage problems.
(3) polymer dielectric of the invention is compared to conventional polymer electrolyte, it is easy to synthesize, with higher ion
Electrical conductivity environmental protection, in the opto-electronic device application causes optics to keep higher photoelectric properties and photoelectric transformation efficiency.
(4) present invention also provides new application direction for hybrid inorganic-organic two-dimensional material simultaneously.
Specific embodiment
For the ease of understanding the present invention, more comprehensively, meticulously retouch to inventing to do herein below in conjunction with preferred embodiment
State, but protection scope of the present invention is not limited to specific examples below.
Unless otherwise defined, all technical terms used hereinafter are generally understood that implication phase with those skilled in the art
Together.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to limit the present invention's
Protection domain.
Unless otherwise specified, various raw material, reagent, instrument and equipment used in the present invention etc. can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1：
A kind of used by dye sensitization solar battery polymer dielectric of the present invention, has in the polymer dielectric
Machine-inorganic hybridization two-dimensional material
The used by dye sensitization solar battery method for preparing polymer electrolytes of the present embodiment, comprises the following steps：
(1) 20.45g 1-METHYLPYRROLIDONEs (NMP) are taken, in being put into 60mL brown bottles, 0.4301g agaroses is added4h, stirring speed are stirred under conditions of 80 DEG C of heating water baths
Degree is controlled to 500r/min, forms uniform solution；
(2) after uniform solution cooling prepared by step (1), 0.2782g I are added2With stir under 0.1261g LiI, room temperature
4.3h is mixed, mixing speed is controlled to 500r/min；
(3) the 2% of agarose mass fraction is taken(8.6mg), add in brown bottle, continue to stir 4h under room temperature,
Mixing speed is controlled to 500r/min, obtains polymer dielectric.Test the performance of electrolyte manufactured in the present embodiment：In room temperature
Under environment, platinum electrode is adopted to test electrode, the electrical conductivity for measuring electrolyte is 3.32 × 10-3S/cm。
Using knife coating procedure by TiO2Slip (solid-liquid mass ratio 1:7) conductive glass surface is coated on, is allowed to film forming, Jing
After 500 DEG C are heat-treated 35 minutes, it is put into and is dissolved with 0.4 × 10-3In the ethanol solution of mol/LN719 dyestuffs, at room temperature
Sensitization 12h, makes the TiO of dye sensitization2Light anode.
Polymer dielectric manufactured in the present embodiment is added dropwise into the TiO of the dye sensitization in above-mentioned preparation2In light anode, put
In entering vacuum drying chamber, be warming up to 80 DEG C, be incubated 1h so that polymer dielectric be contracted to it is thick, along with to electrode, after
Continue and toast 1h at 85 DEG C, make polymeric dye sensitization solar battery.Test the performance of the DSSC：
In room temperature environment, using xenon lamp simulated solar irradiation, light intensity is 80mW/cm2(light intensity：Condition is demarcated using silicon photoelectric diode
Under), polymeric dye sensitization solar battery is measured, effective illuminating area is 0.25cm2Photoelectric transformation efficiency be 2.73%.
Embodiment 2：
A kind of used by dye sensitization solar battery polymer dielectric of the present invention, has in the polymer dielectric
Machine-inorganic hybridization two-dimensional material
The used by dye sensitization solar battery method for preparing polymer electrolytes of the present embodiment, comprises the following steps：
(1) 20.32g 1-METHYLPYRROLIDONEs (NMP) are taken, in being put into 60mL brown bottles, 0.4301g agaroses is added4h, stirring speed are stirred under conditions of 80 DEG C of heating water baths
Degree is controlled to 550r/min, forms uniform solution；
(2) after uniform solution cooling prepared by step (1), 0.2753gI is added2With 0.1246gLiI, stir under room temperature
4.3h, mixing speed is controlled to 550r/min；
(3) the 3% of agarose mass fraction is taken(12.96mg), add in brown bottle, continue to stir under room temperature
4.5h, mixing speed is controlled to 550r/min, obtains polymer dielectric.Test the performance of the polymer dielectric：In room temperature
Under environment, platinum electrode is adopted to test electrode, the electrical conductivity for measuring electrolyte is 4.38 × 10-3S/cm。
Using knife coating procedure by TiO2Slip (solid-liquid mass ratio 1:7) conductive glass surface is coated on, is allowed to film forming, Jing
After 500 DEG C are heat-treated 35 minutes, it is put into and is dissolved with 0.4 × 10-3In the ethanol solution of mol/LN719 dyestuffs, at room temperature
Sensitization 12h, obtains the TiO of dye sensitization2Light anode.
Polymer dielectric manufactured in the present embodiment is added dropwise into the TiO of the dye sensitization in above-mentioned preparation2In light anode, put
In entering vacuum drying chamber, be warming up to 80 DEG C, be incubated 1h so that polymer dielectric be contracted to it is thick, along with to electrode, after
Continue and toast 1h at 85 DEG C, make polymeric dye sensitization solar battery.Test the polymeric dye sensitization solar battery
Performance：In room temperature environment, using xenon lamp simulated solar irradiation, light intensity is 80mW/cm2(light intensity：Using silicon photoelectric diode mark
Under fixed condition), polymeric dye sensitization solar battery is measured, effective illuminating area is 0.25cm2Photoelectric transformation efficiency be
3.23%.
Embodiment 3：
A kind of used by dye sensitization solar battery polymer dielectric of the present invention, has in the polymer dielectric
Machine-inorganic hybridization two-dimensional material
The used by dye sensitization solar battery method for preparing polymer electrolytes of the present embodiment, comprises the following steps：
(1) preparation of electrolyte：20.26g 1-METHYLPYRROLIDONEs (NMP) are taken, in being put into 60mL brown bottles, is added
0.4301g agarosesIn the condition of 80 DEG C of heating water baths
Lower stirring 4h, mixing speed is controlled to 600r/min, forms uniform solution；
(2) after uniform solution cooling prepared by step (1), 0.2725g I are added2With stir under 0.1267g LiI, room temperature
4.3h is mixed, mixing speed is controlled to 600r/min；
(3) agarose mass fraction 2% is takenIn adding brown bottle, continue to stir 4.8h under room temperature, stir
It is 600r/min to mix speeds control, that is, obtain polymer dielectric.Test the performance of the polymer dielectric：In room temperature environment
Under, platinum electrode is adopted to test electrode, the electrical conductivity for measuring electrolyte is 5.27 × 10-3S/cm。
Using knife coating procedure by TiO2Slip (solid-liquid mass ratio 1:7) conductive glass surface is coated on, is allowed to film forming, Jing
After 500 DEG C are heat-treated 35 minutes, it is put into and is dissolved with 0.4 × 10-3In the ethanol solution of mol/LN719 dyestuffs, at room temperature
Sensitization 12h, obtains the TiO of dye sensitization2Light anode.
Polymer dielectric manufactured in the present embodiment is added dropwise into the TiO of the dye sensitization in above-mentioned preparation2In light anode, put
In entering vacuum drying chamber, be warming up to 80 DEG C, be incubated 1h so that polymer dielectric be contracted to it is thick, along with to electrode, after
Continue and toast 1h at 85 DEG C, make polymeric dye sensitization solar battery.Test the polymeric dye sensitization solar battery
Performance：In room temperature environment, using xenon lamp simulated solar irradiation, light intensity is 80mW/cm2(light intensity：Using silicon photoelectric diode mark
Under fixed condition), polymeric dye sensitization solar battery is measured, effective illuminating area is 0.25cm2Photoelectric transformation efficiency be
4.13%.
Embodiment 4：
A kind of used by dye sensitization solar battery polymer dielectric of the present invention, has in the polymer dielectric
Machine-inorganic hybridization two-dimensional material
The used by dye sensitization solar battery method for preparing polymer electrolytes of the present embodiment, comprises the following steps：
(1) 20.32g 1-METHYLPYRROLIDONEs (NMP) are taken, in being put into 60mL brown bottles, 0.4301g agaroses is added5h is stirred under conditions of 80 DEG C of heating water baths, is stirred
Speeds control is 650r/min, forms uniform solution；
(2) after uniform solution cooling prepared by step (1), 0.2713g I are added2With stir under 0.1253g LiI, room temperature
4.3h is mixed, mixing speed is controlled to 650r/min；
(3) the 3% of agarose mass fraction is takenIn adding brown bottle, continue to stir 5.3h under room temperature, stir
It is 650r/min to mix speeds control, obtains polymer dielectric.Test the performance of the polymer dielectric：Under room temperature environment,
Platinum electrode is adopted to test electrode, the electrical conductivity for measuring electrolyte is 7.43 × 10-3S/cm。
Using knife coating procedure by TiO2Slip (solid-liquid mass ratio 1:7) conductive glass surface is coated on, is allowed to film forming, Jing
After 500 DEG C are heat-treated 35 minutes, it is put into and is dissolved with 0.4 × 10-3In the ethanol solution of mol/LN719 dyestuffs, at room temperature
Sensitization 12h, obtains the TiO of dye sensitization2Light anode.
Polymer dielectric manufactured in the present embodiment is added dropwise into the TiO of the dye sensitization in above-mentioned preparation2In light anode, put
In entering vacuum drying chamber, be warming up to 80 DEG C, be incubated 1h so that polymer dielectric be contracted to it is thick, along with to electrode, after
Continue and toast 1h at 85 DEG C, make polymeric dye sensitization solar battery.Test the polymeric dye sensitization solar battery
Performance：In room temperature environment, using xenon lamp simulated solar irradiation, light intensity is 80mW/cm2(light intensity：Using silicon photoelectric diode mark
Under fixed condition), polymeric dye sensitization solar battery is measured, effective illuminating area is 0.25cm2Photoelectric transformation efficiency be
4.85%.
Embodiment 5：
A kind of used by dye sensitization solar battery polymer dielectric of the present invention, has in the polymer dielectric
Machine-inorganic hybridization two-dimensional material
The used by dye sensitization solar battery method for preparing polymer electrolytes of the present embodiment, comprises the following steps：
(1) 20.25g 1-METHYLPYRROLIDONEs (NMP) are taken, in being put into 60mL brown bottles, 0.4301g agaroses is added4h, stirring speed are stirred under conditions of 80 DEG C of heating water baths
Degree is controlled to 700r/min, forms uniform solution；
(2) after uniform solution cooling prepared by step (1), 0.2658g I are added2With stir under 0.1211g LiI, room temperature
4.5h is mixed, mixing speed is controlled to 700r/min；
(3) the 4% of agarose mass fraction is takenIn adding brown bottle, continue to stir under room temperature
5.8h, mixing speed is controlled to 700r/min, obtains polymer dielectric.Test the performance of the polymer dielectric：In room temperature
Under environment, platinum electrode is adopted to test electrode, the electrical conductivity for measuring electrolyte is 4.35 × 10-3S/cm。
Using knife coating procedure by TiO2Slip (solid-liquid mass ratio 1:7) conductive glass surface is coated on, is allowed to film forming, Jing
After 500 DEG C are heat-treated 35 minutes, it is put into and is dissolved with 0.4 × 10-3In the ethanol solution of mol/L N719 dyestuffs, at room temperature
Sensitization 12h, obtains the TiO of dye sensitization2Light anode.
Polymer dielectric manufactured in the present embodiment is added dropwise into the TiO of the dye sensitization in above-mentioned preparation2In light anode, put
In entering vacuum drying chamber, be warming up to 80 DEG C, be incubated 1h so that polymer dielectric be contracted to it is thick, along with to electrode, after
Continue and toast 1h at 85 DEG C, make polymeric dye sensitization solar battery.
The performance of the polymeric dye sensitization solar battery obtained by test the present embodiment：In room temperature environment, using xenon
Lamp simulated solar irradiation, light intensity is 80mW/cm2(light intensity：Under the conditions of being demarcated using silicon photoelectric diode), measure polymeric dye quick
Change solar cell, effective illuminating area is 0.25cm2Photoelectric transformation efficiency be 3.96%.
Comparative example 1：
Hybrid inorganic-organic two dimension material is not contained in the used by dye sensitization solar battery polymer dielectric of this comparative example
Material, its concrete preparation method is comprised the following steps：
(1) 20.25g 1-METHYLPYRROLIDONEs (NMP) are taken, in being put into 60mL brown bottles, 0.4301g agaroses is added4h is stirred under conditions of 80 DEG C of heating water baths, is stirred
Speeds control is 600r/min；
(2) 0.2658g I are added2With 5h is stirred under 0.1211g LiI, room temperature, mixing speed is controlled to 600r/min, obtains
To electrolyte.Test the performance of the polyelectrolyte：Under room temperature environment, platinum electrode is adopted to test electrode, measure electrolyte
Electrical conductivity is 2.39 × 10-3S/cm。
Using knife coating procedure by TiO2Slip (solid-liquid mass ratio 1:7) conductive glass surface is coated on, is allowed to film forming, Jing
After 500 DEG C are heat-treated 35 minutes, it is put into and is dissolved with 0.4 × 10-3In the ethanol solution of mol/LN719 dyestuffs, at room temperature
Sensitization 12h, obtains the TiO of dye sensitization2Light anode.
Electrolyte manufactured in the present embodiment is added dropwise into the TiO of the dye sensitization in above-mentioned preparation2In light anode, vacuum is put into
In drying box, be warming up to 80 DEG C, be incubated 1h so that polymer dielectric be contracted to it is thick, along with to electrode, continuing 85
1h is toasted at DEG C, polymeric dye sensitization solar battery is made.
Test the performance of the DSSC of this comparative example：In room temperature environment, using xenon lamp simulated solar
Light, light intensity is 80mW/cm2(light intensity：Under the conditions of being demarcated using silicon photoelectric diode), the DSSC is measured,
Effectively illuminating area is 0.25cm2Photoelectric transformation efficiency be 1.94%.
Knowable to the experimental result of comparative example 1 and embodiment 1-5, through the addition of hybrid inorganic-organic two-dimensional material,
So that the photoelectric efficiency of polymeric dye sensitization solar battery is at least increased to 2.73% by 1.94%, electrical conductivity is also by 2.39
×10-3S/cm rises at least to 3.32 × 10-3S/cm.Work as selectionIts shared agarose mass fraction is
During 3wt.%, ideal electrolytic conductivity and photoelectric efficiency are obtained, respectively 7.43 × 10-3S/cm and 4.85%.
Comparative example 2：
The used by dye sensitization solar battery polymer dielectric of this comparative example, it adopts the complicated binary mistake of preparation process
Metal oxide two-dimensional material is crossed, the specific preparation method of the polymer dielectric is comprised the following steps：
(1) 20.25g 1-METHYLPYRROLIDONEs (NMP) are taken to be put in 60mL brown bottles, 0.4301g agaroses are added4h, mixing speed are stirred under conditions of 80 DEG C of heating water baths
It is controlled to 700r/min；
(2) 0.2982g I are added2With 4h is stirred under 0.1261g LiI, room temperature, mixing speed is controlled to 700r/min, plus
Enter 0.0133g transiton metal binary oxides ZnCo2O4Two-dimensional material (preparation method reference Ionics., 2016,1-6), room temperature
Lower stirring 4h, mixing speed is controlled to 700r/min, obtains the polymer dielectric of agar glycosyl.Test the polymer dielectric
Performance：Under room temperature environment, platinum electrode is adopted to test electrode, the electrical conductivity for measuring electrolyte is 3.31 × 10-3S/cm。
Using knife coating procedure by TiO2Slip (solid-liquid mass ratio 1:7) conductive glass surface is coated on, is allowed to film forming, Jing
After 500 DEG C are heat-treated 35 minutes, 0.4 × 10 is put into-3In the N719 dyestuff ethanol solutions of mol/L, it is sensitized at room temperature
12h, obtains the TiO of dye sensitization2Light anode.
Polymer dielectric prepared by this comparative example is added dropwise the TiO of the dye sensitization in above-mentioned preparation2In light anode, put
In entering vacuum drying chamber, be warming up to 80 DEG C, be incubated 1h so that polymer dielectric be contracted to it is thick, along with to electrode, after
Continue and toast 1h at 85 DEG C, make polymeric dye sensitization solar battery.
Test the performance of the polymeric dye sensitization solar battery obtained by this comparative example：In room temperature environment, using xenon
Lamp simulated solar irradiation, light intensity is 80mW/cm2(light intensity：Under the conditions of being demarcated using silicon photoelectric diode), measure polymeric dye quick
Change solar cell, effective illuminating area is 0.25cm2Photoelectric transformation efficiency be 2.47%.
Knowable to the Comparison of experiment results of comparative example 2 and embodiment 1-5, if the hybrid inorganic-organic of the present invention is two-dimentional
Material is replaced by the more complicated transiton metal binary oxides two-dimensional material of preparation process, gained DSSC
Photoelectric efficiency is only 2.47%, and electrolytic conductivity is 3.31 × 10-3S/cm, and the electrolytic conductivity of the present invention at least also reaches
To 3.32 × 10-3S/cm, cell photoelectric efficiency is 2.73% (embodiment 1)；And the electrical conductivity of the electrolyte of the present invention is even
7.43 × 10 can be reached-3S/cm, photoelectric transformation efficiency can reach 4.85% (see embodiment 2), far above the electrolysis of this comparative example
The electrical conductivity and photoelectric transformation efficiency of matter.As can be seen here, not only synthetic method is simple for polymer dielectric of the invention, cost
Low, electrical conductivity is high, is also greatly improved using the photoelectric properties of the DSSC of the polymer dielectric.
To sum up, the synthetic method of used by dye sensitization solar battery polymer dielectric of the invention is simple, and electrical conductivity is high,
Low cost, stability and high efficiency.Using the DSSC of Inventive polymers electrolyte, short-circuit current density and open circuit
Voltage has increase, finally improves the photoelectric efficiency of DSSC.
Claims (10)
1. a kind of used by dye sensitization solar battery polymer dielectric, it is characterised in that add in the polymer dielectric
Hybrid inorganic-organic two-dimensional material, the hybrid inorganic-organic two-dimensional material is selected fromIn
One or more.
2. a kind of method for preparing polymer electrolytes as claimed in claim 1, it is characterised in that comprise the following steps：
(1) agarose is added in 1-METHYLPYRROLIDONE, is stirred under the conditions of constant temperature water bath, form uniform solution；
(2) after uniform solution cooling prepared by step (1), iodine and salt compounded of iodine is added to continue to stir at normal temperatures；
(3) hybrid inorganic-organic two-dimensional material is added, stirs to it and be completely dissolved, that is, complete the system of the polymer dielectric
It is standby.
3. preparation method as claimed in claim 2, it is characterised in that the structure of the agarose is：
4. preparation method as claimed in claim 2, it is characterised in that the addition of the agarose is 1-METHYLPYRROLIDONE
3wt.%～the 4.5wt.% of quality.
5. preparation method as claimed in claim 2, it is characterised in that the salt compounded of iodine selected from lithium iodide, one kind of sodium iodide or
It is several.
6. preparation method as claimed in claim 2, it is characterised in that the addition of the iodine is 1-METHYLPYRROLIDONE
0.12wt.%～the 0.15wt.% of quality；The salt compounded of iodine is 1～1.5 with the molar ratio of iodine.
7. preparation method as claimed in claim 2, it is characterised in that the addition of the hybrid inorganic-organic two-dimensional material
For the 2wt.%～4wt.% of agarose.
8. the preparation method as described in any one of claim 2-7, it is characterised in that in the step (1), bath temperature is 70
～90 DEG C, mixing speed is 500～700r/min, and mixing time is 3.5～5h.
9. the preparation method as described in any one of claim 2-7, it is characterised in that in the step (2), mixing speed is
500～700r/min, the time of stirring is 3.5～5h.
10. the preparation method as described in any one of claim 2-7, it is characterised in that in the step (3), mixing speed is
500～700r/min, the time of stirring is 4～6h.
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|---|---|---|---|---|
| CN1564328A (en) * | 2004-04-22 | 2005-01-12 | 复旦大学 | Solar cel adopting organic/inorganic nano doped quasi-solid state electrolyte, and its prepn. method |
| CN103219157A (en) * | 2012-12-24 | 2013-07-24 | 长兴化学工业股份有限公司 | Electrolyte composition for dye-sensitized solar cell |
| CN105513800A (en) * | 2015-12-25 | 2016-04-20 | 中南大学 | Preparation method of low-cost quasi solid electrolyte for dye sensitized solar cell |
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2016
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1564328A (en) * | 2004-04-22 | 2005-01-12 | 复旦大学 | Solar cel adopting organic/inorganic nano doped quasi-solid state electrolyte, and its prepn. method |
| CN103219157A (en) * | 2012-12-24 | 2013-07-24 | 长兴化学工业股份有限公司 | Electrolyte composition for dye-sensitized solar cell |
| CN105513800A (en) * | 2015-12-25 | 2016-04-20 | 中南大学 | Preparation method of low-cost quasi solid electrolyte for dye sensitized solar cell |
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| YING YANG等: ""Magnetic field processed solid-state dye-sensitized solar cells with nickel oxide modified agarose electrolyte"", 《JOURNAL OF POWER SOURCES》 * |
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