CN106783191A - Quasi-solid electrolyte for DSSC and preparation method thereof - Google Patents
Quasi-solid electrolyte for DSSC and preparation method thereof Download PDFInfo
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- CN106783191A CN106783191A CN201611261201.2A CN201611261201A CN106783191A CN 106783191 A CN106783191 A CN 106783191A CN 201611261201 A CN201611261201 A CN 201611261201A CN 106783191 A CN106783191 A CN 106783191A
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- tunica fibrosa
- electric spinning
- quasi
- spinning polymer
- solution
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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 18
- 229920000642 polymer Polymers 0.000 claims abstract description 76
- 238000009987 spinning Methods 0.000 claims abstract description 62
- 239000002608 ionic liquid Substances 0.000 claims abstract description 37
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 18
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 39
- 239000003792 electrolyte Substances 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 229960003638 dopamine Drugs 0.000 claims description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 16
- 239000010703 silicon Substances 0.000 claims description 16
- 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 11
- 235000013675 iodine Nutrition 0.000 claims description 11
- 239000000377 silicon 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
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000005693 optoelectronics Effects 0.000 abstract description 2
- 230000009466 transformation Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 42
- 238000000034 method Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 229910052740 iodine Inorganic materials 0.000 description 8
- 239000011630 iodine Substances 0.000 description 8
- 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
- 238000001523 electrospinning Methods 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-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
- 239000007788 liquid Substances 0.000 description 5
- 230000007774 longterm Effects 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000007787 solid 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
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- -1 levodopa amine Chemical class 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical class CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 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
- 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
- 150000002148 esters Chemical class 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
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920005594 polymer fiber Polymers 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
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical class NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 241001502050 Acis Species 0.000 description 1
- HWIUYZBEKKGMCW-UHFFFAOYSA-N CN1CN(C=C1)CCCC.I(=O)(=O)O Chemical group CN1CN(C=C1)CCCC.I(=O)(=O)O HWIUYZBEKKGMCW-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
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 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
- 239000008151 electrolyte solution Substances 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
- 229960004502 levodopa Drugs 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 238000005191 phase separation Methods 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
- 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
- H01G9/20—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
The invention discloses solid electrolyte for DSSC and preparation method thereof.Quasi-solid electrolyte for DSSC of the invention, it includes three-dimensional netted electric spinning polymer tunica fibrosa, and nano silicon and ionic liquid on the electric spinning polymer tunica fibrosa are carried on, the modification of nano silicon significantly improves optoelectronic transformation efficiency when as DSSC.
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, environment-friendly, making is simple, as 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 there is the performance steady in a long-term of solid electrolyte, so as to be widely used in
Prepare the quasi-solid-state dye sensitized solar cell of stability and high efficiency.Compared to other quasi-solid electrolytes, ionic liquid benchmark is consolidated
State electrolyte as one of quasi-solid electrolyte by paying close attention to especially because ionic liquid at room temperature have electrical conductivity high and
The advantages of electrochemical window is wide, and organic solvent low boiling point, volatile defect can be overcome.However, because ionic liquid exists
Liquid condition is still within room temperature, therefore there is easily leakage, influence the long-time stability of battery.In recent years, it is
Overcome the ionic liquid easy leakage problem of reference solid state electrolyte, researcher with 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, new quasi-solid electrolyte is prepared using electrospinning, overcomes the problem of electrolyte easily leakage, improves the steady in a long-term of battery
Property be this area research emphasis and challenge.
In the 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 is higher.
A kind of quasi-solid electrolyte for DSSC, it is characterised in that it includes three-dimensional netted
Electric spinning polymer tunica fibrosa, and it is carried on nano silicon and ionic liquid on the electric spinning polymer tunica fibrosa.
Further, the thickness of the electric spinning polymer tunica fibrosa is 40~80 microns.
Further, the porosity of the electric spinning polymer tunica fibrosa is 40~80%.
Further, the material of the electric spinning polymer tunica fibrosa is Kynoar.
Further aspect of the present invention is to provide a kind of preparation of quasi-solid electrolyte for DSSC
Method, the electricity conversion of the quasi-solid electrolyte obtained by the preparation method is higher.
A kind of quasi-solid electrolyte stated as described above, comprises the following steps：
An electric spinning polymer tunica fibrosa is provided, the electric spinning polymer tunica fibrosa is formed by polymer solution electrostatic spinning；
In impregnated in silicon source solution by the electric spinning polymer tunica fibrosa, nanometer titanium dioxide is obtained by collosol and gel
Silicon shape loads electric spinning polymer tunica fibrosa；
And, nano silicon shape load electric spinning polymer tunica fibrosa is immersed in ionic liquid electrolyte.
Further, before electric spinning polymer tunica fibrosa carries out the step of impregnated in silicon source solution, also including by electrospinning
Polymer fiber film impregnated in dopamine solution.
Further, the levodopa amine aqueous solution is the Tris- hydrochloric acid solutions of dopamine.
Further, the dip time of the precursor solution that impregnated in silica is 20~28h.
Further, the polymer solution constitutes solvent by PVDF is dissolved in by acetone and DMF
The solution for being formed.
Further, the ionic liquids ionic liquids electrolyte includes 0.3~0.7mol/L elemental iodines.
Quasi-solid electrolyte for DSSC of the invention, it includes three-dimensional netted electrospinning polymerization
Fibres film, and it is carried on nano silicon and ionic liquid on the electric spinning polymer tunica fibrosa, nanometer titanium dioxide
The modification of silicon significantly improves optoelectronic transformation efficiency when as DSSC.
Brief description of the drawings
Fig. 1 is the obtained quasi-solid electrolyte based on silicon dioxide modified PVDF electrospun fiber membranes of the embodiment of the present invention 1
DSSC device is applied in 100mW/cm2Illumination condition under voltage-current density curve map；
Fig. 2 is the obtained quasi-solid electrolyte based on silicon dioxide modified PVDF electrospun fiber membranes of the embodiment of the present invention 2
DSSC device is applied in 100mW/cm2Illumination condition under voltage-current density curve map；
Fig. 3 is the obtained quasi-solid electrolyte based on silicon dioxide modified PVDF electrospun fiber membranes of the embodiment of the present invention 3
DSSC device is applied in 100mW/cm2Illumination condition under voltage-current density curve map.
Specific embodiment
Unless otherwise defined, all technologies used herein and scientific terminology have and 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, composition, step, method comprising listed elements,
Product or device are not necessarily limited to those key elements, and can be including not expressly listed other key elements or this kind of composition, step
Suddenly, method, product or the intrinsic key element of 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 be closed, it is not included the material in addition to the material that those are described, but relative
Except customary impurities.When phrase " by ... constitute " be rather than immediately following after theme in the clause that appears in claim main body
When, it 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 any 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 number range is described herein, unless otherwise indicated, otherwise the scope is intended to include its end
Value and all integers and fraction within the range.
" 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 that the mass parts of component A are a parts, the matter of B component
Amount part is b parts, then it represents that the quality of component A and the mass ratio a of B component：b.Or, the quality for representing component A is 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 limitation.
"and/or" is used to represent that one of illustrated situation or both may to occur, for example, A and/or B includes (A
And B) and (A or B)；
Additionally, the indefinite article " one kind " and " one " before key element of the present invention or 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 include plural form, unless the obvious purport of the quantity refers to singulative.
Quasi-solid electrolyte for DSSC of the invention, it includes three-dimensional netted electrospinning polymerization
Fibres film, and it is carried on nano silicon and ionic liquid on the electric spinning polymer tunica fibrosa
Above-mentioned term " electric spinning polymer tunica fibrosa " refer to by by polymer fiber using the fibre obtained by electrostatic spinning
Dimension film.Herein, " electrostatic spinning " is by thousands of to up to ten thousand volt high-pressure electrostatics, powered polymer on polymer solution or melt band
Drop is accelerated in the presence of electric field force in the Taylor conical points of capillary.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 fibrofelt for being similar to non-woven cloth-like.
Used as electric spinning polymer tunica fibrosa of the invention, it 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 tunica fibrosa is prevented and is using liquid
Make working electrode 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 tunica fibrosa 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 tunica fibrosa polymerizable material can include Kynoar (PVDF), PTFE, PVA,
The instantiations such as CMC, NMP, are preferably PVDF in the present invention.
Explainable nano silicon once is in the load configuration of electric spinning polymer tunica fibrosa.Nano silicon is most of
Particle is coated on the filametntary surface of electric spinning polymer tunica fibrosa.The bases such as the hydroxyl that nano silicon passes through 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 that it is distributed in the mesh of electric spinning polymer tunica fibrosa.These mesh energy
Very strong polarity and Coulombian field is 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 electric spinning polymer tunica fibrosa of the invention, such as 40 microns, 45 micro-
Rice, 50 microns, 60 microns, 70 microns, 75 microns or 80 microns.
As the porosity of electric spinning polymer tunica fibrosa of the invention 40~80%, such as 40%, 45%, 50%, 60%,
70%th, 75% or 80% etc..Herein, porosity refers to that block or film material mesopore volume is total in its natural state with material
The percentage of volume, porosity includes true porosity, closes 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 tunica fibrosa is provided, the electric spinning polymer tunica fibrosa is formed by polymer solution electrostatic spinning；
In impregnated in silicon source solution by the electric spinning polymer tunica fibrosa, nanometer titanium dioxide is obtained by collosol and gel
Silicon shape loads electric spinning polymer tunica fibrosa；
And, nano silicon shape load electric spinning polymer tunica fibrosa is immersed in ionic liquid.
In above-mentioned preparation method, before electric spinning polymer tunica fibrosa carries out the step of impregnated in silicon source solution, also wrap
Include during electric spinning polymer tunica fibrosa impregnated in into dopamine solution.The dipping of dopamine solution, can improve nano-particle in electricity
The load fastness of spinning polymer tunica fibrosa.Its reason is, contained amino, carboxyl isopolarity group meeting in dopamine solution
With reference on the surface of nano-silicon dioxide particle.These polar groups can be by hydrogen bond action and the boundary of electric spinning polymer tunica fibrosa
Face phase separation, to improve the adhesive force of the two.
Above-mentioned dopamine solution refers to that dopamine is dissolved in resulting solution in liquid solvent.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 nano-particle in the load fastness of electric spinning polymer tunica fibrosa, 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) aminomethanes
L) with the mixed liquor of hydrochloric acid solution.Hydroxyl contained by Tris- hydrochloric acid solutions can improve the surface polarity of nano-particle, to reach
Strengthen with the load fastness of electric spinning polymer tunica fibrosa.
In the present invention, impregnated in the silicon source solution of silica referring to property of dip time for 20~28h, such as 20h,
22h, 24h, 26h, 27h or 28h etc..As for the temperature of dipping, can adopt carry out under normal temperature.
Above-mentioned silicon source refers to the general designation containing the organo-silicon compound that nano silicon can be formed by sol-gal process.
Silicon source can be esters of silicon acis, such as TEOS.
Here, be dissolved in organic solvent for ester type compound or metal alkoxide by sol-gal process, forms uniform solution, so
After add other components, at a certain temperature reaction form gel, most afterwards through dried process.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 conventional form that component included in silicon source solution can be commonly used, is the implementation method of TEOS such as in silicon source
In, it can also be comprising acid or alkali (ammoniacal liquor) or solvent (ethanol etc.).
During electric spinning polymer tunica fibrosa is prepared, polymer solution is dissolved in by acetone and N, N- diformazan for PVDF
Base formamide constitutes the solution that solvent is formed.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 liquids.
Herein, BMII ionic liquids refer to 1- butyl -3- methylimidazole salt compounded of iodine.Herein, 1- butyl -3- methylimidazoles salt compounded of iodine also known as
It is iodate -1- butyl -3- methylimidazoles, its No. CAS is 65039-05-6, and its molecular structural formula isWhen
So, ionic liquid can also use other conventional forms of this area.
Below do not address part and be applied to prior art.
Embodiment 1
Step one, preparation electrospinning PVDF tunica fibrosas.Kynoar (PVDF) is dissolved in acetone and N, N- dimethyl methyl
(weight compares 7 to acid amides：3) PVDF polymer solutions are prepared in mixed solution.It is stirred 24 hours in agitator and is made
It is completely dissolved, and ultrasonically treated 30 minutes to form polymer solution, the polymer solution that will be formed introduces 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 is fine
Dimension film.
Step 2, the PVDF tunica fibrosas of 40 micron thickness that will be prepared are immersed in dopamine (DA) Tris- hydrochloric acid solutions
In, obtain DPA@PVDF tunica fibrosas.
Step 3, DPA@pvdf membranes are put into ethanol, ammoniacal liquor and water mixed solution, strong agitation, are added after 30min
TEOS, continues to stir 20h, and reaction terminates, and obtains the SiO that nano silicon shape loads electric spinning polymer tunica fibrosa2@DPA@
PVDF tunica fibrosas.
Step 4, by above-mentioned SiO2@DPA@PVDF tunica fibrosas 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 tunica fibrosas.Kynoar (PVDF) is dissolved in acetone and N, N- dimethyl methyl
(weight compares 7 to acid amides：3) PVDF polymer solutions are prepared in mixed solution.It is stirred 24 hours in agitator and is made
It is completely dissolved, and ultrasonically treated 30 minutes to form polymer solution, the polymer solution that will be formed introduces 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 is fine
Dimension film.
Step 2, the PVDF tunica fibrosas of 60 micron thickness that will be prepared are immersed in dopamine (DA) Tris- hydrochloric acid solutions
In, obtain DPA@PVDF tunica fibrosas.
Step 3, DPA@pvdf membranes are put into ethanol, ammoniacal liquor and water mixed solution, strong agitation, are added after 30min
TEOS, continues to stir 28h, and reaction terminates, and obtains the SiO that nano silicon shape loads electric spinning polymer tunica fibrosa2@DPA@
PVDF tunica fibrosas.
Step 4, by above-mentioned SiO2@DPA@PVDF tunica fibrosas 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 tunica fibrosas.Kynoar (PVDF) is dissolved in acetone and N, N- dimethyl methyl
(weight compares 7 to acid amides：3) PVDF polymer solutions are prepared in mixed solution.It is stirred 24 hours in agitator and is made
It is completely dissolved, and ultrasonically treated 30 minutes to form polymer solution, the polymer solution that will be formed introduces 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 is fine
Dimension film.
Step 2, the PVDF tunica fibrosas of 80 micron thickness that will be prepared are immersed in dopamine (DA) Tris- hydrochloric acid solutions
In, obtain DPA@PVDF tunica fibrosas.
Step 3, DPA@pvdf membranes are put into ethanol, ammoniacal liquor and water mixed solution, strong agitation, are added after 30min
TEOS, continues to stir 24h, and reaction terminates, and obtains the SiO that nano silicon shape loads electric spinning polymer tunica fibrosa2@DPA@
PVDF tunica fibrosas.
Step 4, by above-mentioned SiO2@DPA@PVDF tunica fibrosas 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 quasi-solid electrolyte prepared according to embodiment 1~3 assembles the photoelectric characteristic of DSSC device
Measurement.Voltage-current density is simulated under standard conditions (AM1.5,100mW/cm2,25 DEG C) by using a solar energy
Device (PEC-L11, PECCELL) is measured, and wherein the solar simulator is by installing the xenon lamp and Keithley of 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 7.6%,
Open-circuit voltage (Voc) is 0.71V, and short circuit current close (Jsc) is 16.63mA.cm-2, fill factor, curve factor (FF) is 64%.Embodiment 2
The electricity conversion of prepared quasi-solid electrolyte is 8.0%, and open-circuit voltage (Voc) is 0.71V, and short circuit current is close
(Jsc) it is 17.10mA.cm-2, fill factor, curve factor (FF) is 66%.The photoelectric conversion effect of the quasi-solid electrolyte prepared by embodiment 3
Rate is 8.2%, and open-circuit voltage (Voc) is 0.72V, and short circuit current close (Jsc) is 17.89mA.cm-2, fill factor, curve factor (FF) is
64%.
Because the number range of each technological parameter involved in the present invention can not possibly all embody in the above-described embodiments,
As long as but those skilled in the art's envisioned any numerical value fallen into the above-mentioned number range completely can implement this
Invention, also includes any combination 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 number range, this disclosure for being not to be construed as technical scheme is not filled
Point.
Applicant states that the present invention illustrates detailed process equipment of the invention and technological process by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, do 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 protection of the invention
In the range of.
Claims (10)
1. a kind of quasi-solid electrolyte for DSSC, it is characterised in that it includes three-dimensional netted electricity
Spinning polymer tunica fibrosa, and it is carried on nano silicon and ionic liquid on the electric spinning polymer tunica fibrosa.
2. quasi-solid electrolyte according to claim 1, it is characterised in that the thickness of the electric spinning polymer tunica fibrosa is
40~80 microns.
3. quasi-solid electrolyte according to claim 1, it is characterised in that the porosity of the electric spinning polymer tunica fibrosa
40~80%.
4. quasi-solid electrolyte according to claim 1, it is characterised in that the material of the electric spinning polymer tunica fibrosa is
Kynoar.
5. the preparation method of a kind of quasi-solid electrolyte as described in Claims 1 to 4 any one, it is characterised in that including
Following steps：
An electric spinning polymer tunica fibrosa is provided, the electric spinning polymer tunica fibrosa is formed by polymer solution electrostatic spinning；
In impregnated in silicon source solution by the electric spinning polymer tunica fibrosa, nano silicon shape is obtained by collosol and gel
Load electric spinning polymer tunica fibrosa；
And, nano silicon shape load electric spinning polymer tunica fibrosa is immersed in ionic liquid electrolyte.
6. preparation method according to claim 5, it is characterised in that carry out impregnated in silicon source in electric spinning polymer tunica fibrosa
Before the step of solution, also including electric spinning polymer tunica fibrosa impregnated in into dopamine solution in.
7. preparation method according to claim 6, it is characterised in that the dopamine solution is the Tris- salt of dopamine
Acid solution.
8. preparation method according to claim 5, it is characterised in that the leaching of the silicon source solution that impregnated in silica
The stain time is 20~28h.
9. preparation method according to claim 1, it is characterised in that the polymer solution is dissolved in by acetone for PVDF
The solution that solvent is formed is constituted with DMF.
10. preparation 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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| EP1521277A2 (en) * | 2003-10-01 | 2005-04-06 | Korea Institute of Science and Technology | Solid state dye-sensitized solar cell employing composite polymer electrolyte |
| CN102013516A (en) * | 2010-10-22 | 2011-04-13 | 浙江大学 | Porous fiber gel polymer electrolyte and preparation method thereof |
| CN103268955A (en) * | 2013-01-23 | 2013-08-28 | 浙江地坤键新能源科技有限公司 | Composite gel polymer electrolyte and preparation method and application thereof |
| KR101381705B1 (en) * | 2013-04-24 | 2014-04-07 | 한국생산기술연구원 | Dye-sensitized solar cell comprising hybrid nano fibers by electrospinning and sprayng as a polymer electrolyte, and the fabrication method thereof |
| CN104393336A (en) * | 2014-11-13 | 2015-03-04 | 湘潭大学 | Nano composite fiber-reinforced gel polymer electrolyte and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1521277A2 (en) * | 2003-10-01 | 2005-04-06 | Korea Institute of Science and Technology | Solid state dye-sensitized solar cell employing composite polymer electrolyte |
| CN102013516A (en) * | 2010-10-22 | 2011-04-13 | 浙江大学 | Porous fiber gel polymer electrolyte and preparation method thereof |
| CN103268955A (en) * | 2013-01-23 | 2013-08-28 | 浙江地坤键新能源科技有限公司 | Composite gel polymer electrolyte and preparation method and application thereof |
| KR101381705B1 (en) * | 2013-04-24 | 2014-04-07 | 한국생산기술연구원 | Dye-sensitized solar cell comprising hybrid nano fibers by electrospinning and sprayng as a polymer electrolyte, and the fabrication method thereof |
| CN104393336A (en) * | 2014-11-13 | 2015-03-04 | 湘潭大学 | Nano composite fiber-reinforced gel polymer electrolyte and preparation method thereof |
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