CN106531446A - Quasi-solid electrolyte for dye-sensitized solar cell and preparation method thereof - Google Patents
Quasi-solid electrolyte for dye-sensitized solar cell and preparation method thereof Download PDFInfo
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- fibrous membrane
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002608 ionic liquid Substances 0.000 claims abstract description 37
- 229920000642 polymer Polymers 0.000 claims description 74
- 239000012528 membrane Substances 0.000 claims description 71
- 238000009987 spinning Methods 0.000 claims description 60
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 41
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 34
- 239000003792 electrolyte Substances 0.000 claims description 21
- 229960003638 dopamine Drugs 0.000 claims description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 15
- 229910052719 titanium Inorganic materials 0.000 claims description 15
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical class [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 9
- 235000013675 iodine Nutrition 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 230000005611 electricity Effects 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000010041 electrostatic spinning Methods 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims 1
- 238000002386 leaching Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 238000001523 electrospinning Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 4
- 229920005594 polymer fiber Polymers 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 7
- 229910052681 coesite Inorganic materials 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 229910052740 iodine Inorganic materials 0.000 description 6
- 239000011630 iodine Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 5
- METIGIXCFPEQNM-UHFFFAOYSA-M amino-(2-bromoethyl)-dimethylazanium;bromide Chemical compound [Br-].C[N+](C)(N)CCBr METIGIXCFPEQNM-UHFFFAOYSA-M 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000007774 longterm Effects 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- -1 amino, carboxyl Chemical group 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 235000019445 benzyl alcohol Nutrition 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- HWIUYZBEKKGMCW-UHFFFAOYSA-N CN1CN(C=C1)CCCC.I(=O)(=O)O Chemical compound CN1CN(C=C1)CCCC.I(=O)(=O)O HWIUYZBEKKGMCW-UHFFFAOYSA-N 0.000 description 1
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002496 iodine Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910009112 xH2O Inorganic materials 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- H01G9/0029—Processes of manufacture
- H01G9/0036—Formation of the solid electrolyte layer
-
- 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)
- Manufacturing & Machinery (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Nonwoven Fabrics (AREA)
- Hybrid Cells (AREA)
Abstract
The invention discloses a quasi-solid electrolyte for a dye-sensitized solar cell and a preparation method thereof. The quasi-solid electrolyte for the dye-sensitized solar cell comprises three-dimensional netty electrospinning polymer fiber film, and nano titanium dioxide and ionic liquid loaded on the three-dimensional netty electrospinning polymer fiber film. When a modification effect of the nano titanium dioxide is carried out on the dye-sensitized solar cell, a photoelectric conversion rate is clearly improved.
Description
Technical field
The present invention relates to the technical field of electrolyte, in particular to for DSSC
Quasi-solid electrolyte and preparation method thereof.
Background technology
DSSC has the advantages that cheap, environmental friendliness, makes simple, becomes the third generation sun
The representative of energy battery.DSSC is constituted by dye sensitization light anode, electrolyte and to three parts of electrode, its
Middle electrolyte is played an important role during reducing dyes regeneration or hole transport.
Quasi-solid electrolyte be it is a kind of between liquid electrolyte and it is all solid state between gel state electrolyte, it can maximum limit
Degree ground keeps the high mobility of liquid electrolyte, while the performance steady in a long-term with solid electrolyte, so as to be widely used in
Prepare the quasi-solid-state dye sensitized solaode of stability and high efficiency.Compared to other quasi-solid electrolytes, ionic liquid benchmark is solid
State electrolyte as one of quasi-solid electrolyte by paying close attention to especially, this is because ionic liquid at room temperature have electrical conductivity high and
The advantages of electrochemical window width, and organic solvent low boiling point, volatile defect can be overcome.However, as ionic liquid exists
Liquid condition is still within room temperature, therefore there is easily leakage, affect the long-time stability of battery.In recent years, it is
Overcome ionic liquid reference solid state electrolyte easy leakage problem, research worker organic molecule, inorganic nanoparticles and
High molecular polymer is used as gel, the ionic liquid for preparing respectively-organic molecule quasi-solid electrolyte, ionic liquid-nothing
Machine nano-particle quasi-solid electrolyte and ionic liquid-high molecular polymer quasi-solid electrolyte to a certain extent can with gram
The problem of ionic liquid electrolyte easily leakage is taken, but still is difficult to solve the long term stability problem of ionic liquid electrolyte.Cause
This, prepares new quasi-solid electrolyte using electrospinning, the problem for overcoming electrolyte easily to reveal, and improves the steady in a long-term of battery
Property be this area research emphasis and challenge.
In prior art, the electricity conversion of quasi-solid electrolyte is limited.
The content of the invention
In view of this, one aspect of the present invention is to provide a kind of quasi- solid state electrolysis for DSSC
Matter, the electricity conversion of the solid electrolyte are higher.
A kind of quasi-solid electrolyte for DSSC, it is characterised in which includes three-dimensional netted
Electric spinning polymer fibrous membrane, and the nano titanium oxide that is carried on the electric spinning polymer fibrous membrane and ionic liquid.
Further, the thickness of the electric spinning polymer fibrous membrane is 40～80 microns.
Further, the porosity of the electric spinning polymer fibrous membrane is 40～80%.
Further, the material of the electric spinning polymer fibrous membrane is Kynoar.
Further aspect of the present invention is to provide a kind of preparation of the quasi-solid electrolyte for DSSC
Method, the electricity conversion of the quasi-solid electrolyte obtained by the preparation method are higher.
A kind of quasi-solid electrolyte stated as described above, comprises the following steps：
An electric spinning polymer fibrous membrane is provided, the electric spinning polymer fibrous membrane is formed by polymer solution electrostatic spinning；
The electric spinning polymer fibrous membrane is carried out impregnated in titanium source solution, nanometer titanium dioxide is obtained by collosol and gel
Titanium shape loads electric spinning polymer fibrous membrane；
And, nano titanium oxide shape load electric spinning polymer fibrous membrane is immersed in ionic liquid electrolyte.
Further, before electric spinning polymer fibrous membrane carries out the step of impregnated in titanium source solution, also include electrospinning
Polymer fiber film is impregnated in dopamine solution.
Further, Tris- hydrochloric acid solution of the dopamine solution for dopamine.
Further, the dip time of the precursor solution that impregnated in titanium dioxide is 1.5～2.5h.
Further, the polymer solution is dissolved in by PVDF and constitutes solvent by acetone and DMF
The solution for being formed.
Further, the ionic liquids ionic liquids electrolyte includes 0.3～0.7mol/L elemental iodines.
The quasi-solid electrolyte for DSSC of the present invention, which includes three-dimensional netted electrospinning polymerization
Fibres film, and the nano titanium oxide that is carried on the electric spinning polymer fibrous membrane and ionic liquid, nanometer titanium dioxide
The modification of titanium significantly improves optoelectronic transformation efficiency when as DSSC.
Description of the drawings
Fig. 1 is the 1 obtained quasi-solid electrolyte that PVDF electrospun fiber membranes are modified based on titanium dioxide of the embodiment of the present invention
DSSC device is applied in 100mW/cm2Illumination condition under voltage-current density curve chart；
Fig. 2 is the 2 obtained quasi-solid electrolyte that PVDF electrospun fiber membranes are modified based on titanium dioxide of the embodiment of the present invention
DSSC device is applied in 100mW/cm2Illumination condition under voltage-current density curve chart；
Fig. 3 is the 3 obtained quasi-solid electrolyte that PVDF electrospun fiber membranes are modified based on titanium dioxide of the embodiment of the present invention
DSSC device is applied in 100mW/cm2Illumination condition under voltage-current density curve chart.
Specific embodiment
Unless otherwise defined, all technologies used herein and scientific terminology with the common skill of art of the present invention
The identical implication that art personnel are generally understood that.When there is contradiction, the definition in this specification is defined.
Term as used herein：
" by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " including ", " having ", " containing "
Or its any other deformation, it is intended that cover including for non-exclusionism.For example, the compositionss comprising listed elements, step, method,
Product or device are not necessarily solely those key elements, and can be including other not expressly listed key element or this kind of compositionss, step
Suddenly, the intrinsic key element of method, product or device.
Conjunction " by ... constitute " exclude any key element do not pointed out, step or component.If be used in claim,
This phrase will make claim for closed so as to not comprising the material in addition to the material that those describe, but relative
Except customary impurities.When phrase " by ... constitute " be rather than immediately following theme in the clause that occurs in claim main body after
When, which is only limited to the key element described in the clause；Other key elements be not excluded as the overall claim it
Outward.
Equivalent, concentration or other values or parameter are excellent with scope, preferred scope or a series of upper limit preferred values and lower limit
During the Range Representation that choosing value is limited, this is appreciated that and specifically discloses by any range limit or preferred value and any scope
All scopes that arbitrary pairing of lower limit or preferred value is formed, regardless of whether whether the scope separately discloses.For example, when open
During scope " 1～5 ", described scope should be interpreted as including scope " 1～4 ", " 1～3 ", " 1～2 ", " 1～2 and 4～
5 ", " 1～3 and 5 " etc..When numerical range is described herein, unless otherwise indicated, otherwise the scope is intended to include its end
Value and all integers within the range and fraction.
" mass parts " refer to the basic measurement unit of the mass ratio relation for representing multiple components, and 1 part can represent arbitrary list
Position quality, can such as be expressed as 1g, may also indicate that 2.689g etc..If we say component A mass parts be a parts, the matter of B component
Amount part is b parts, then it represents that mass ratio a of the quality and B component of component A：b.Or, represent component A quality be aK, B groups
The quality divided is bK (K is Arbitrary Digit, represents multiplying factor).Can not misread, and unlike mass fraction, all components
Mass parts sum be not limited to 100 parts of restriction.
"and/or" is used to represent that one of illustrated situation or both may to occur, and for example, A and/or B include (A
And B) and (A or B)；
Additionally, key element of the present invention or indefinite article " one kind " and " one " before component are to key element or the quantitative requirement of component
(i.e. occurrence number) unrestriction.Therefore " one " or " one kind " should be read as including one or at least one, well and odd number
The key element or component of form also includes plural form, unless the obvious purport of the quantity refers to singulative.
The quasi-solid electrolyte for DSSC of the present invention, which includes three-dimensional netted electrospinning polymerization
Fibres film, and the nano titanium oxide that is carried on the electric spinning polymer fibrous membrane and ionic liquid
Above-mentioned term " electric spinning polymer fibrous membrane " is referred to by polymer fiber to be utilized the fibre obtained by electrostatic spinning
Dimension film.Herein, " electrostatic spinning " is by thousand of to up to ten thousand volt high-pressure electrostatics, powered polymer on polymer solution or melt band
Drop is accelerated in the Taylor conical points of capillary tube in the presence of electric field force.When electric field force is sufficiently large, polymer drop
Surface tension is overcome to form injection thread.Thread solvent evaporation or solidification in course of injection, finally fall on the reception device, shape
Into the fiber felt for being similar to non-woven cloth-like.
Used as the electric spinning polymer fibrous membrane of the present invention, which has the effect of following several respects：First, electric spinning polymer is fine
Dimension film has three-dimensional net structure, can provide bigger specific surface area, can play a part of " solidification " ionic liquid, and so it can
More effectively to include and inject electrolyte ion, the mobility of ionic liquid is reduced, improve the long-term steady of electrolyte
It is qualitative, and the quasi-solid electrolyte uniform component distribution for preparing.Secondly, electric spinning polymer fibrous membrane is prevented and is using liquid
Working electrode is made in the DSSC of electrolyte by the leakage of liquid electrolyte and to connecting between electrode
Touch the short circuit for causing.Therefore, it can solve long-term steady in conventional liquid or semi-solid DSSC
Qualitative question.3rd, the three-dimensional net structure of electric spinning polymer fibrous membrane is greatly improved the dye sensitization of solar of preparation
The mechanical performance of battery, while three-dimensional net structure can provide orderly ion channel for ion diffusion, is favorably improved electrolysis
The electrical conductivity and ionic mobility of matter.
Formed electric spinning polymer fibrous membrane polymerizable material can include Kynoar (PVDF), PTFE, PVA,
The instantiations such as CMC, NMP, are preferably PVDF in the present invention.
Can illustratively nano titanium oxide in the load configuration of electric spinning polymer fibrous membrane.Nano titanium oxide is most of
Particle is coated on the filametntary surface of electric spinning polymer fibrous membrane.The bases such as hydroxyl of the nano titanium oxide by its particle surface
The filametntary interface of group's effect, therefore its attachment is more firm.For the mode of coating, its load is more firm.
The load configuration of ionic liquid can be which is distributed in the mesh of electric spinning polymer fibrous membrane.These mesh energy
Very strong polarity and Coulombian field are provided, and ionic liquid shows the polarity for increasing, and is thus firmly attached in mesh.It is logical
Often, the size of these mesh is molecular level, the referred to as preferable passage of transport ions liquid.
Preferably it is 40～80 microns as the thickness of the electric spinning polymer fibrous membrane of the present invention, such as 40 microns, 45 micro-
Rice, 50 microns, 60 microns, 70 microns, 75 microns or 80 microns.
As the present invention electric spinning polymer fibrous membrane porosity 40～80%, such as 40%, 45%, 50%, 60%,
70%th, 75% or 80% etc..Herein, porosity refers to that bulk or film material mesopore volume are total in its natural state with material
The percentage ratio of volume, porosity include true porosity, close porosity and first porosity.
The preparation method of the above-mentioned quasi-solid electrolyte of the present invention, comprises the following steps：
An electric spinning polymer fibrous membrane is provided, the electric spinning polymer fibrous membrane is formed by polymer solution electrostatic spinning；
The electric spinning polymer fibrous membrane is carried out impregnated in titanium source solution, nanometer titanium dioxide is obtained by collosol and gel
Titanium shape loads electric spinning polymer fibrous membrane；
And, nano titanium oxide shape load electric spinning polymer fibrous membrane is immersed in ionic liquid.
In above-mentioned preparation method, before electric spinning polymer fibrous membrane carries out the step of impregnated in titanium source solution, also wrap
Include and electric spinning polymer fibrous membrane is impregnated in dopamine solution.The dipping of dopamine solution, can improve nanoparticle in electricity
The load fastness of spinning polymer fibrous membrane.Its reason is, contained amino, carboxyl isopolarity group meeting in dopamine solution
With reference on the surface of nano-titania particle.These polar groups can pass through the boundary of hydrogen bond action and electric spinning polymer fibrous membrane
Face phase separation, to improve the adhesive force of the two.
Above-mentioned dopamine solution refer to dopamine be dissolved in liquid solvent obtained by solution.Herein, dopamine chemistry
Entitled 4- (2- ethylamino-s) benzene -1,2- diphenol, referred to as " DA ", its No. CAS is 51-61-6.
In order to further improve nanoparticle in the load fastness of electric spinning polymer fibrous membrane, dopamine solution is many
The Tris- hydrochloric acid solutions of bar amine.Herein, Tris- hydrochloric acid solutions refer to that (its concentration is 0.05mol/ to three (methylol) aminomethane
L) the mixed liquor with hydrochloric acid solution.Hydroxyl contained by Tris- hydrochloric acid solutions can improve the surface polarity of nanoparticle, to reach
Strengthen the load fastness with electric spinning polymer fibrous membrane.
In the present invention, it is 1.5～2.5h with impregnated in the referring to property of dip time of the titanium source solution of titanium dioxide, such as
1.5h, 1.75h, 2h, 2.25h or 2.5h etc..As for the temperature of dipping, can adopt.
Above-mentioned titanium source refers to the general designation containing the compound that nano titanium oxide can be formed by sol-gal process.Titanium source can
Think titanate esters, such as TBOT (butyl titanate) etc..
Here, sol-gal process is dissolved in ester type compound or metal alkoxide in organic solvent, forms uniform solution, so
After add other components, reaction at a certain temperature forms gel, and last drying is processed.The basic reaction of sol-gal process
It is as follows：Its most basic reaction is：(l) hydrolysis：M(OR)n+xH2O → M (OH) x (OR) n-x+xROH；(2) it is polymerized anti-
Should：- M-OH+HO-M- →-M-O-M-+H2O ,-M-OR+HO-M- →-M-O-M-+ROH.
The form of the routine that the component included in titanium source solution can be commonly used, such as in the embodiment that titanium source is TBOT
In, which can also include acid or alkali, and solvent (benzyl alcohol, ethanol etc.).
During electric spinning polymer fibrous membrane is prepared, polymer solution is dissolved in by acetone and N, N- diformazan for PVDF
The solution formed by the constituted solvent of base Methanamide.Herein, the volume ratio of acetone and DMF can be 7：3.
Above-mentioned ionic liquid electrolyte refers to the electrolyte solution comprising ionic liquid.Its except comprising ionic liquid it
Outward, 0.3～0.7mol/L elemental iodines, such as 0.3mol/L, 0.35mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/ can also be included
L、0.7mol/L。
Ionic liquid included in ionic liquid electrolyte can be imidazolium ionic liquid, such as BMII ionic liquid
Body.Herein, BMII ionic liquids refer to 1- butyl -3- Methylimidazole. iodine salt.Herein, 1- butyl -3- methyl miaows
Azoles iodine salt also known as be iodate -1- butyl -3- Methylimidazole .s, its No. CAS is 65039-05-6, and its molecular structural formula isCertainly, ionic liquid can also adopt other conventional forms of this area.
Below do not address part and be applied to prior art.
Embodiment 1
Step one, preparation electrospinning PVDF fibrous membrane.Kynoar (PVDF) is dissolved in into acetone and N, N- dimethyl methyl
(weight compares 7 to amide：3) PVDF polymer solutions are prepared in mixed solution.Which is stirred into 24 hours in agitator and is made
Which is completely dissolved, and supersound process 30 minutes is to form polymer solution, and the polymer solution for being formed is introduced Static Spinning
Spinning is carried out in silk device and to the polymer solution.Control spinning time 2 h, the PVDF for preparing 40 micron thickness are fine
Dimension film.
Step 2, the PVDF fibrous membranes of 40 micron thickness for preparing are immersed in into dopamine (DA) Tris- hydrochloric acid solutions
In, obtain DPA@PVDF fibrous membranes.
Step 3, DPA@pvdf membranes are put in benzyl alcohol and alcohol mixed solution, strong agitation, after be slowly added to TBOT
With the mixed solution of ethanol, continue stirring 1.5h, reaction terminates, obtain nano titanium oxide shape load electric spinning polymer fibrous membrane
SiO2@DPA@PVDF fibrous membranes.
Step 4, by above-mentioned SiO2@DPA@PVDF fibrous membranes are immersed in the ionic liquid electrolyte containing iodine (by 0.3mol/L
Elemental iodine and BMII ionic liquids and solvent are constituted) in, until being impregnated with completely, form quasi-solid electrolyte.
Embodiment 2
Step one, preparation electrospinning PVDF fibrous membrane.Kynoar (PVDF) is dissolved in into acetone and N, N- dimethyl methyl
(weight compares 7 to amide：3) PVDF polymer solutions are prepared in mixed solution.Which is stirred into 24 hours in agitator and is made
Which is completely dissolved, and supersound process 30 minutes is to form polymer solution, and the polymer solution for being formed is introduced Static Spinning
Spinning is carried out in silk device and to the polymer solution.4 hours spinning time of control, the PVDF for preparing 60 micron thickness are fine
Dimension film.
Step 2, the PVDF fibrous membranes of 60 micron thickness for preparing are immersed in into dopamine (DA) Tris- hydrochloric acid solutions
In, obtain DPA@PVDF fibrous membranes.
Step 3, DPA@pvdf membranes are put in benzyl alcohol and alcohol mixed solution, strong agitation, after be slowly added to TBOT
With the mixed solution of ethanol, continue stirring 2.5h, reaction terminates, obtain nano titanium oxide shape load electric spinning polymer fibrous membrane
SiO2@DPA@PVDF fibrous membranes.
Step 4, by above-mentioned SiO2@DPA@PVDF fibrous membranes are immersed in the ionic liquid electrolyte containing iodine (by 0.7mol/L
Elemental iodine and BMII ionic liquids and solvent are constituted) in, until being impregnated with completely, form quasi-solid electrolyte.
Embodiment 3
Step one, preparation electrospinning PVDF fibrous membrane.Kynoar (PVDF) is dissolved in into acetone and N, N- dimethyl methyl
(weight compares 7 to amide：3) PVDF polymer solutions are prepared in mixed solution.Which is stirred into 24 hours in agitator and is made
Which is completely dissolved, and supersound process 30 minutes is to form polymer solution, and the polymer solution for being formed is introduced Static Spinning
Spinning is carried out in silk device and to the polymer solution.6 hours spinning time of control, the PVDF for preparing 80 micron thickness are fine
Dimension film.
Step 2, the PVDF fibrous membranes of 80 micron thickness for preparing are immersed in into dopamine (DA) Tris- hydrochloric acid solutions
In, obtain DPA@PVDF fibrous membranes.
Step 3, DPA@pvdf membranes are put in benzyl alcohol and alcohol mixed solution, strong agitation, after be slowly added to TBOT
With the mixed solution of ethanol, continue stirring 2h, reaction terminates, obtain nano titanium oxide shape load electric spinning polymer fibrous membrane
SiO2@DPA@PVDF fibrous membranes.
Step 4, by above-mentioned SiO2@DPA@PVDF fibrous membranes are immersed in the ionic liquid electrolyte containing iodine (by 0.5mol/L
Elemental iodine and BMII ionic liquids and solvent are constituted) in, until being impregnated with completely, form quasi-solid electrolyte.
The photoelectric characteristic of DSSC device is assembled according to quasi-solid electrolyte prepared by embodiment 1～3
Measurement.Voltage-current density is simulated by using a solar energy under standard conditions (AM1.5,100mW/cm2,25 DEG C)
Device (PEC-L11, PECCELL) is measured, wherein xenon lamp and Keithley of the solar simulator by installation 150W
And it is corrected using the silion cell of standard.
Refer to Fig. 1, Fig. 2 and Fig. 3.The electricity conversion of the quasi-solid electrolyte prepared by embodiment 1 is 7.4%,
Open-circuit voltage (Voc) is 0.69V, and short circuit current close (Jsc) is 17.58mA.cm-2, fill factor, curve factor (FF) is 61%.Embodiment 2
The electricity conversion of prepared quasi-solid electrolyte is 7.9%, and open-circuit voltage (Voc) is 0.70V, and short circuit current is close
(Jsc) it is 17.85mA.cm-2, fill factor, curve factor (FF) is 63%.The photoelectric conversion effect of the quasi-solid electrolyte prepared by embodiment 3
Rate is 7.5%, and open-circuit voltage (Voc) is 0.69V, and short circuit current close (Jsc) is 16.89mA.cm-2, fill factor, curve factor (FF) is
65%.
As the numerical range of each technological parameter involved in the present invention all can not possibly embody in the above-described embodiments,
As long as but those skilled in the art's envisioned any numerical value fallen in the above-mentioned numerical range completely can implement this
Invention, also includes the combination in any of occurrence in the range of some numerical value certainly.Herein, for the consideration of length, eliminate to
Go out the embodiment of occurrence in certain one or more numerical range, this disclosure for being not to be construed as technical scheme is not filled
Point.
Applicant states that the present invention illustrates the detailed process equipment of the present invention and technological process by above-described embodiment,
But above-mentioned detailed process equipment and technological process are the invention is not limited in, that is, does not mean that the present invention has to rely on above-mentioned detailed
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
Addition, concrete mode selection to the equivalence replacement and auxiliary element of each raw material of product of the present invention etc., falls in the protection of the present invention
In the range of.
Claims (10)
1. a kind of quasi-solid electrolyte for DSSC, it is characterised in which includes three-dimensional netted electricity
Spinning polymer fibrous membrane, and the nano titanium oxide that is carried on the electric spinning polymer fibrous membrane and ionic liquid.
2. quasi-solid electrolyte according to claim 1, it is characterised in that the thickness of the electric spinning polymer fibrous membrane is
40～80 microns.
3. quasi-solid electrolyte according to claim 1, it is characterised in that the porosity of the electric spinning polymer fibrous membrane
40～80%.
4. quasi-solid electrolyte according to claim 1, it is characterised in that the material of the electric spinning polymer fibrous membrane is
Kynoar.
5. a kind of preparation method of the quasi-solid electrolyte as described in Claims 1 to 4 any one, it is characterised in that include
Following steps：
An electric spinning polymer fibrous membrane is provided, the electric spinning polymer fibrous membrane is formed by polymer solution electrostatic spinning；
The electric spinning polymer fibrous membrane is carried out impregnated in titanium source solution, nano titanium oxide shape is obtained by collosol and gel
Load electric spinning polymer fibrous membrane；
And, nano titanium oxide shape load electric spinning polymer fibrous membrane is immersed in ionic liquid electrolyte.
6. preparation method according to claim 5, it is characterised in that carry out impregnated in titanium source in electric spinning polymer fibrous membrane
Before the step of solution, also include electric spinning polymer fibrous membrane being impregnated in dopamine solution.
7. preparation method according to claim 6, it is characterised in that Tris- salt of the dopamine solution for dopamine
Acid solution.
8. preparation method according to claim 5, it is characterised in that the leaching of the titanium source solution that impregnated in titanium dioxide
The stain time is 1.5～2.5h.
9. preparation method according to claim 1, it is characterised in that the polymer solution is dissolved in by acetone for PVDF
The solution formed by solvent constituted with DMF.
10. manufacture method according to claim 1, it is characterised in that the ionic liquid electrolyte comprising 0.3～
0.7mol/L elemental iodines.
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