CN101630593B - Electrolyte solution and application of same in dye-sensitized solar battery - Google Patents
Electrolyte solution and application of same in dye-sensitized solar battery Download PDFInfo
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- CN101630593B CN101630593B CN 200910165603 CN200910165603A CN101630593B CN 101630593 B CN101630593 B CN 101630593B CN 200910165603 CN200910165603 CN 200910165603 CN 200910165603 A CN200910165603 A CN 200910165603A CN 101630593 B CN101630593 B CN 101630593B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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- 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
- Y02E10/549—Organic PV cells
Abstract
The invention provides an electrolyte solution and an application of the same in a dye-sensitized solar battery. The general formula of a redox couple of the electrolyte solution is nA+((A-A)<2+>B2)+mM+x(C<+>D<->)+yIS+zG, wherein A and (A-A)<2+>B2 respectively represent reducing material and oxidizing material in the redox couple; M represents organic solvent, C<+>D<-> represents ion liquid, IS represents inorganic salt, G represents additive in the electrolyte; n is the mol ratio of the A and the (A-A)<2+>B2 in the redox couple, and m, x, y and z respectively represent mol ratios of the organic solvent, the ion liquid, the inorganic salt and the additive to the (A-A)<2+>B2. The invention also provides the application of the electrolyte solution in the redox couple to the preparation of the dye-sensitized solar battery. The redox couple has excellent performance, no corrosion, and better electron transfer characteristic on a carbon electrode.
Description
Technical field
The present invention relates to DSSC and make the field.Particularly, the present invention relates to contain the electrolyte solution of oxidation-reduction pair (1,1,3,3-tetramethyl thiourea and disulphide thereof), and the application in DSSC.
Background technology
From engineering college of Swiss Confederation in 1991
After professor proposed DSSC (DSCs), this type of battery had been subjected to extensive concern in the world.The DSCs battery has that the prices of raw and semifnished materials are cheap, the simple relative higher advantage with battery efficiency of manufacture craft, be that the promising low cost of a class, environmental pollution are little, the novel solar battery of excellent performance (O ' Regan, B.;
, M.Nature 1991,353,737-740).The DSCs battery is by receiving brilliant TiO
2Light anode, electrolyte and electrode three parts are constituted, wherein electrolytical main effect is that hole transport is given electrode and reduction-oxidation attitude dye molecule.At present, high efficiency DSCs battery all is based on and contains I
3 -/ I
-The liquid electrolyte of oxidation-reduction pair realizes that this mainly is because I
3 -/ I
-Electricity is to having comparatively ideal kinetic advantage in battery, promptly on to electrode, and I
3 -→ I
-Reduction reaction speed enough fast, and I
3 -Ion and TiO
2The reaction speed of the recombination reaction of electronics (dark reaction) is very slow in the perforated membrane conduction band.But in fact, I
3 -/ I
-Electricity is to being not optimal charge transfer medium, and mainly there is following problem in it: (1) elemental iodine all has corrosiveness to most metals, especially the most frequently used silver that arrives and platinum in the battery.If long-time the use contained I
3 -/ I
-The electrolyte of oxidation-reduction pair causes the reduction and the shorter battery life of stability test easily; Technology of preparing to battery has also proposed harsher requirement simultaneously, has increased battery cost.(2) iodine has certain vapour pressure, equally the Sealing Technology of battery is had higher requirement, and is unfavorable for the practical application of battery.(3) I
3 -/ I
-Electricity is to absorbing a certain amount of visible light.(4) I
3 -/ I
-Oxidation-reduction potential has limited the maximum open circuit voltage of battery, is unfavorable for further improving battery efficiency.
At above problem, people attempt substituting I with other forms of oxidation-reduction pair
3 -/ I
-, as: (1) single electron ferrocene (Fc
+/0) system, although their energy fast restore oxidation state dye molecules, dark reaction speed is faster, efficient is extremely low, and (J.Phys.Chem.B 2001,105,1422-1429) for Gregg, people such as B.A..(2) pseudohalogen oxidation-reduction pair (SeCN)
2/ SeCN
-Deng, being assembled into the IPCE of battery and photoelectric conversion efficiency, all very low (J.Phys.Chem.B 2001,105 for Oskam, people such as G., 6867-6873).(3) Co (II/III)-multi-pyridine ligand is as Co (dbbiP)
2(ClO
4)
2, Co (dmbip)
2] (ClO
4)
2Deng (dbbip=2,6-bis (1 '-butyl-benzimidazol-2 '-y1) pyridine, dmbip=2,6-bis (1 '-methyl-benzimidazol-2 '-y1) pyridine), when this compounds is used for the DSCs battery, though photoelectric conversion efficiency is greatly improved (at the low light level by force down), some Co (II) compound simultaneously also can be with reducing dyes, thereby has reduced the stability (Hattori of battery, S. etc., J.Am.Chem.Soc.2005,127,9648-9654; Sapp, S.A. etc., J.Am.Chem.Soc.2002,124,11215-11222; Nusbaumer, H. etc., Chem.Eur.J.2003,9,3756-3763).(4) organic free radical 2,2,6, when 6-tetramethyl-1-piperidinyloxy is used for the DSCs battery, exist equally the poor stability of battery problem (Zhang, Z. etc., Adv.Funct.Mater.2008,18,341-346).And the non-preferably iodine oxidation-reduction pair of stability, battery efficiency is undesirable, and (european patent application: EP1856522A2), all above-mentioned documents are here quoted as a reference in full for Yasuteru, S. etc.
Therefore, the non-iodine oxidation-reduction pair of research low cost, high efficiency, good stability is one of development trend of DSSC.
Summary of the invention
Employed term among the present invention unless otherwise noted, is to understand according to its conventional sense.
Term used in the present invention " non-iodine oxidation-reduction pair " refers to I
3 -/ I
-The substitute that electricity is right.Non-iodine oxidation-reduction pair among the present invention refers to 1,1,3,3-tetramethyl thiourea (A) and contain the disulphide ([A-A] of different balance anions
2+B
2).The present invention is only with A and [A-A]
2+(TFSI)
2The application example explanation that makes an explanation, wherein, TFSI
-Be two (trifluoromethyl sulphonyl) imines ion.
Term as used herein " based on the DSSC of carbon to electrode " refers to the carbon electrode DSSC of doing electrode.
One object of the present invention is to provide a kind of electrolyte solution that comprises function admirable, non-corrosiveness oxidation-reduction pair, and this oxidation-reduction pair shows excellent electron transfer characteristic on carbon electrode.
Another object of the present invention is to provide the above-mentioned application of electrolyte solution in the preparation DSSC that comprises function admirable, non-corrosiveness oxidation-reduction pair.
Another purpose of the present invention is to provide and comprises the above-mentioned DSSC that contains the electrolyte solution of function admirable, non-corrosiveness oxidation-reduction pair.
On the one hand, the invention provides a kind of electrolyte solution that is used for DSSC, this electrolyte solution contains oxidation-reduction pair, and the general formula that this oxidation-reduction pair is formed is:
nA+([A-A]
2+B
2)
Wherein, A is the reduced form component in the oxidation-reduction pair, and its structure is as follows:
[A-A]
2+B
2Be the oxidized form component in the oxidation-reduction pair, its cationic formation and structure are by shown in the following formula:
[A-A]
2+Structure is as follows:
B is a balance anion, and B is selected from halide ion, perchlorate, tetrafluoride boron ion, phosphorus hexafluoride ion, antimony fluoride ion, nitrate ion, two (fluorine sulphonyl) imines ion, two (trifluoromethyl sulphonyl) imines ion, (fluorine sulphonyl) (trifluoromethyl sulphonyl) imines ion and hexafluoro niobium ion; Described halide ion is preferably chloride ion and/or bromide ion; N is A and [A-A]
2+B
2Mol ratio, and 0.01≤n≤500.
Described electrolyte solution also contains organic solvent M, and this organic solvent M is selected from nitrile, for example acetonitrile, propionitrile, 3-methoxypropionitrile, 3-hydroxypropionitrile; Alcohols, for example methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols, octanol, ethylene glycol, glycerol, 1,2-propylene glycol, 1, ammediol; Ester class, for example dimethyl carbonate, diethyl carbonate, propene carbonate, methyl formate, Ethyl formate, butyl formate, ethyl acetate, methyl benzoate, ethyl benzoate, repefral, diethyl phthalate; Oxolane and composition thereof; M is described organic solvent M and [A-A]
2+B
2Mol ratio, and 10≤m≤2000.
Described electrolyte solution also contains ionic liquid C
+D
-, C wherein
+Be selected from imidazoles cation, pyrazoles cation, pyridines cation, piperidines cation, pyroles cation, indoles cation, carbazoles cation, quaternaries cation, trialkyl sulfonium cationoid and composition thereof; D
-Be selected from halide ion (Cl
-, Br
-), tetrafluoride boron ion, phosphorus hexafluoride ion, antimony fluoride ion, perchlorate, nitrate ion, two (fluorine sulphonyl) imines ion, two (trifluoromethyl sulphonyl) imines ion, (fluorine sulphonyl) (trifluoromethyl sulphonyl) imines ion, hexafluoro niobium ion and composition thereof; Described halide ion is preferably chloride ion and/or bromide ion; X is described ionic liquid C
+D
-With [A-A]
2+B
2Mol ratio, and 0≤x≤2000.
Described electrolyte solution also contains inorganic salts IS, these inorganic salts IS is selected from lithium salts, sodium salt, sylvite, quaternary ammonium salt and composition thereof, and the anion among the described inorganic salts IS is selected from perchlorate, halide ion, tetrafluoride boron ion, phosphorus hexafluoride ion, antimony fluoride ion, nitrate ion, two (fluorine sulphonyl) imines ion, two (trifluoromethyl sulphonyl) imines ion, (fluorine sulphonyl) (trifluoromethyl sulphonyl) imines ion, hexafluoro niobium ion and composition thereof; Described halide ion is preferably chloride ion and/or bromide ion; Y is described inorganic salts IS and [A-A]
2+B
2Mol ratio, and 0≤y≤500.
Preferably, described electrolyte solution can also contain additive G, this additive G is selected from pyridine, the 2-picoline, the 3-picoline, the 4-picoline, the 2-ethylpyridine, 3-ethylpyridine, the 4-ethylpyridine, the 2-tert .-butylpyridine, the 3-tert .-butylpyridine, the 4-tert .-butylpyridine, 2-propyl group pyridine, 3-propyl group pyridine, 4-propyl group pyridine, 2-normal-butyl pyridine, 3-normal-butyl pyridine, 4-normal-butyl pyridine, the 2-pentyl pyridine, the 3-pentyl pyridine, the 4-pentyl pyridine, 2,4, the 6-trimethylpyridine, 2,3, the 5-trimethylpyridine, 2, the 4-lutidines, 2, the 5-lutidines, 3, the 5-lutidines, quinoline, isoquinolin and composition thereof; Z is described additive G and [A-A]
2+B
2Mol ratio, and 0≤z≤500.
Oxidation-reduction pair A and [A-A] of containing of the present invention
2+B
2The conventional method that is well known to those skilled in the art of the preparation method of electrolyte solution, be about to each component and mix, under normal temperature or heating, stir, obtain according to electrolyte solution of the present invention.
On the other hand, the invention provides the application of above-mentioned electrolyte solution in the preparation DSSC.
Another aspect the invention provides the DSSC that comprises above-mentioned electrolyte solution.
Preferably, described DSSC also comprises carbon to electrode, promptly based on the DSSC of carbon to electrode.
Preferably, described carbon comprises substrate and carbon film to electrode, and described substrate is an Inorganic Non-metallic Materials, is preferably electro-conductive glass; Described carbon film is the compound of carbon ball or carbon ball and material with carbon element formation, and described material with carbon element has excellent electric conductivity, and it is selected from conductive carbon black, carbon nano-tube, graphite, and composition thereof.
Described carbon is that 200610114581.7 " a kind of carbon pastes and method for making thereof that is used for DSSC to electrode " disclosed method prepares to electrode according to application number.
Described battery also comprises TiO
2The light anode.
According to conventional method well-known to those skilled in the art with TiO
2The light anode, contain oxidation-reduction pair A and [A-A]
2+B
2Electrolyte solution and carbon electrode is assembled into DSSC.
In a specific embodiments of the present invention, the electrolyte solution that contains non-iodine oxidation-reduction pair provided by the invention, its general formula is:
nA+([A-A]
2+B
2)+mM+x(C
+D
-)+yIS+zG
Wherein, A and [A-A]
2+B
2Represent reduced form and oxidized form component in the non-iodine oxidation-reduction pair respectively, M represents organic solvent, C
+D
-The expression ionic liquid, IS represents inorganic salts, G represents additive in electrolyte; N is A and [A-A]
2+B
2Mol ratio, m, x, y and z represent organic solvent, ionic liquid, inorganic salts and additive and [A-A] respectively
2+B
2Mol ratio.
Described non-iodine oxidation-reduction pair comprises reduced form component A and oxidized form component [A-A]
2+B
2, A and [A-A]
2+Structure as follows:
Balance anion B comprises: halide ion (Cl
-, Br
-), perchlorate (ClO
4 -), tetrafluoride boron ion (BF
4 -), phosphorus hexafluoride ion (PF
6 -), antimony fluoride ion (SbF
6 -), nitrate ion (NO
3 -), two (fluorine sulphonyl) imines ion (FSI
-), two (trifluoromethyl sulphonyl) imines ion (TFSI
-), (fluorine sulphonyl) (trifluoromethyl sulphonyl) imines ion (FTFSI
-) or hexafluoro niobium ion (NbF
6 -).
Described non-iodine oxidation-reduction pair A and [A-A]
2+B
2Mol ratio be 0.01≤n≤500.
Described organic solvent M comprise nitrile (as, acetonitrile, propionitrile, 3-methoxypropionitrile, 3-hydroxypropionitrile etc.), alcohols (as, methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols, octanol, ethylene glycol, glycerol, 1,2-propylene glycol, 1, ammediol etc.), the ester class (as, dimethyl carbonate, diethyl carbonate, propene carbonate, methyl formate, Ethyl formate, butyl formate, ethyl acetate, methyl benzoate, ethyl benzoate, repefral, diethyl phthalate etc.), oxolane and they are with arbitrarily than mixed solvent.Described organic solvent M and [A-A]
2+B
2Mol ratio be 10≤m≤2000.
Described ionic liquid C
+D
-, be C
+With D
-Combination in any.C
+Comprise: imidazoles cation, pyrazoles cation, pyridines cation, piperidines cation, pyroles cation, indoles cation, carbazoles cation, quaternaries cation or trialkyl sulfonium cationoid; D
-Comprise: halide ion (Cl
-, Br
-), tetrafluoride boron ion (BF
4 -), phosphorus hexafluoride ion (PF
6 -), antimony fluoride ion (SbF
6 -), perchlorate (ClO
4 -), nitrate ion (NO
3 -), two (fluorine sulphonyl) imines ion (FSI
-), two (trifluoromethyl sulphonyl) imines ion (TFSI
-), (fluorine sulphonyl) (trifluoromethyl sulphonyl) imines ion (FTFSI
-) or hexafluoro niobium ion (NbF
6 -).Described ionic liquid C
+D
-With [A-A]
2+B
2Mol ratio be 0≤x≤2000.
Described inorganic salts IS comprises lithium salts, sodium salt, sylvite or quaternary ammonium salt, and their anion comprises: perchlorate (ClO
4 -), halide ion (Cl
-, Br
-), tetrafluoride boron ion (BF
4 -), phosphorus hexafluoride ion (PF
6 -), antimony fluoride ion (SbF
6 -), nitrate ion (NO
3 -), two (fluorine sulphonyl) imines ion (FSI
-), two (trifluoromethyl sulphonyl) imines ion (TFSI
-), (fluorine sulphonyl) (trifluoromethyl sulphonyl) imines ion (FTFSI
-) or hexafluoro niobium ion (NbF
6 -).Described inorganic salts IS and [A-A]
2+B
2Mol ratio be 0≤y≤500.
The described additive G that improves the electrolyte performance, comprise: pyridine, the 2-picoline, the 3-picoline, the 4-picoline, the 2-ethylpyridine, 3-ethylpyridine, the 4-ethylpyridine, the 2-tert .-butylpyridine, the 3-tert .-butylpyridine, the 4-tert .-butylpyridine, 2-propyl group pyridine, 3-propyl group pyridine, 4-propyl group pyridine, 2-normal-butyl pyridine, 3-normal-butyl pyridine, 4-normal-butyl pyridine, the 2-pentyl pyridine, the 3-pentyl pyridine, the 4-pentyl pyridine, 2,4, the 6-trimethylpyridine, 2,3, the 5-trimethylpyridine, 2, the 4-lutidines, 2, the 5-lutidines, 3, the 5-lutidines, quinoline or isoquinolin.Described additive G and [A-A]
2+B
2Mol ratio be 0≤z≤500.
The method that the present invention's preparation contains the electrolyte solution of non-iodine oxidation-reduction pair comprises breadboard conventional method, is about to each component and mixes, stirs under normal temperature or heating.
Carbon of the present invention is made of following two parts electrode:
(a) base material is all kinds of electro-conductive glass.
(b) carbon film material is hard carbon ball or hard carbon ball and the compound that the material with carbon element of superior electrical conductivity energy is arranged.Material with carbon element with superior electrical conductivity energy comprises: conductive carbon black, Single Walled Carbon Nanotube, multi-walled carbon nano-tubes or graphite.
The application of the electrolyte solution that contains non-iodine oxidation-reduction pair on the carbon back DSSC that the present invention relates to, the present invention proposes in the world first, comprising:
The electrolyte solution that contains non-iodine oxidation-reduction pair according to the inventive method preparation;
The method that provides according to patent " a kind of carbon pastes and method for making thereof that is used for DSSC to electrode " (application number 200610114581.7) prepares carbon to electrode;
The DSSC that light anode, the electrolyte solution that contains non-iodine oxidation-reduction pair and carbon is assembled into electrode according to the conventional method that is applicable to this area.
Compared with prior art, advantage of the present invention is:
Oxidation-reduction pair provided by the present invention has the advantage that cost of material is lower, synthetic method is simple and convenient, cost is low, and when being used for DSSC, its photoelectric conversion efficiency is higher, especially is better than ferrocene (Fc
+/0), pseudohalogen oxidation-reduction pair (SeCN)
2/ SeCN
-Etc. non-iodine electrolyte system, and than the higher Co of photoelectric conversion efficiency (II/III)-multi-pyridine ligand and organic free radical 2,2,6, non-iodine electrolyte system such as 6-tetramethyl-1-piperidinyloxy, it has the good advantage of stability test.Most important advantage is that this type of non-iodine electrolyte system is particularly useful for that cost is low, the carbon that is fit to large-scale application is to electrode, and this is the most outstanding advantage that do not possess of other non-iodine electrolyte systems at present.
Embodiment
The ionic liquid that the present invention relates to can according to the preparation of the known method of those skilled in the art (
M. etc., J.Electrochem.Soc., 1996,143,3099-3108.), the document with and other document of quoting be incorporated herein by reference in full at this.
The various ion liquid mechanism of action of using in the non-iodine oxidation-reduction pair of the present invention electrolyte solution is identical basically, and by those of skill in the art fully understood.All ion liquid effects provide high conductivity and no boiling characteristics.Any one those of skill in the art can derive other various ion liquid application at an easy rate from a kind of ion liquid application.Therefore, embodiments of the invention only are applied as the example explanation that makes an explanation with the part glyoxaline ion liquid.
The mechanism of action of the inorganic salts that use in the non-iodine oxidation-reduction pair of the present invention electrolyte solution is identical basically, and by those of skill in the art fully understood.The effect of all inorganic salts provides good ionic conduction characteristic.Any one those skilled in the art can be easy to derive the application of other inorganic salts from a kind of application of inorganic salts.Therefore, embodiments of the invention are only with the explanation that makes an explanation of the application example of part inorganic salts.
The employed additive that improves the electrolyte performance in the non-iodine oxidation-reduction pair of the present invention electrolyte solution, its mechanism of action is identical basically, and by those of skill in the art fully understood.The effect of all additives all is the open circuit voltage that is used for improving battery, and then improves the opto-electronic conversion performance of battery.Any one those skilled in the art can derive other Application of Additives from a kind of Application of Additives.Therefore, example of the present invention is only with the explanation that makes an explanation of the application example of portions additive.
Those skilled in the art's known method is adopted in the preparation of DSSC, for example, is not limited to, the use document (
M. etc., J.Am.Chem.Soc., 1993,115,6382-6390) method of Jie Shaoing prepares the brilliant TiO of receiving of needed dye sensitization
2The light anode.Concrete grammar is as follows: the method depositing Ti O that passes through blade coating or silk screen printing on electro-conductive glass
2Film was annealed 30 minutes for 450 ℃.Using such method depositing Ti O
2Film 2～5 times is 10～20 microns until film thickness.At last 450 ℃ of annealing 30 minutes, when temperature is reduced to about 80 ℃, with TiO
2Film steeps into dyestuff RuL
2(NCS)
22H
2O (wherein, L=4,4 '-dicarboxylic acids-2,2 '-bipyridine) ethanolic solution in (concentration 0.3mM).Soak after 12 hours, slide is taken out, clean with ethanol earlier and remove attached to TiO
2The dyestuff on surface, last air blow drying obtains the light anode through dye sensitization.This receives brilliant TiO
2Light anode and carbon are assembled into battery to electrode, the electrolyte solution that contains non-iodine oxidation-reduction pair and measure.Above-mentioned document here is incorporated herein by reference in full.
Below in conjunction with specific embodiment, further set forth the present invention.Be not used in but these embodiment only limit to the present invention is described and limit the scope of the invention.
Embodiment 1
The preparation of 1 electrolyte solution:
With A (0.0001mol-500mol), [A-A]
2+(TFSI)
2(0.01mol-1mol), solvent M (0.01mol-10000mol) and other component mix, stirring and dissolving obtains the described electrolyte solution of title.Described each component is recited in the table 1.
The assembling of 2 batteries and performance test thereof:
Prepared electrolyte is assembled into DSSC with the carbon that adopts the preparation of hard carbon ball material to the light anode of electrode, dye sensitization, and the photoelectrochemical behaviour test result of battery sees Table 1.
Method of measurement:
The photoelectric properties of DSCs battery are used standard A M1.5 simulated solar irradiation, adopt computer-controlled constant potential/galvanostat (Princeton Applied Research, Model 263A) to measure, and illuminating area is 0.15cm
2Except as otherwise noted, photoelectric properties of the present invention are measured and are all carried out under room temperature (25 ℃).
Embodiment 2
1. the preparation of electrolyte solution:
With A (0.0001mol-500mol), [A-A]
2+(TFSI)
2(0.01mol-1mol), solvent M (0.1mol-2000mol), ionic liquid C
+D
-(0-2000mol) and other components mix, stirring and dissolving obtains the described electrolyte solution of title.Described each component is recited in the table 2.
2. the assembling of battery and performance test thereof:
Prepared electrolyte is assembled into DSSC with the carbon that adopts the preparation of hard carbon ball material to the light anode of electrode, dye sensitization, the photoelectrochemical behaviour test result of battery sees Table 2, and method of testing is with reference to method of testing used among the embodiment 1.
Embodiment 3
The preparation of 1 electrolyte solution:
With A (0.0001mol-500mol), [A-A]
2+(TFSI)
2(0.01mol-1mol), solvent M (mix, and stirring and dissolving obtains the described electrolyte solution of title by (0.1mol-2000mol), inorganic salts IS (0-500mol) and other component.Described each component is recited in the table 3.
The assembling of 2 batteries and performance test thereof:
Prepared electrolyte is assembled into DSSC with the carbon that adopts the preparation of hard carbon ball material to the light anode of electrode, dye sensitization, the photoelectrochemical behaviour test result of battery sees Table 3, and method of testing is with reference to method of testing used among the embodiment 1.
Embodiment 4
1. the preparation of electrolyte solution:
With A (0.0001mol-500mol), [A-A]
2+(TFSI)
2(0.01mol-1mol), solvent M (0.1mol-2000mol), additive G (0-500mol) and other component mix, stirring and dissolving obtains the described electrolyte solution of title.Described each component is recited in the table 4.
2. the assembling of battery and performance test thereof:
With prepared electrolyte with the carbon that adopts the preparation of hard carbon ball material to electrode, be assembled into DSSC through the light anode of dye sensitization, the photoelectrochemical behaviour test result of battery sees Table 4, and method of testing is with reference to method of testing used among the embodiment 1.
Embodiment 5
1. the preparation of electrolyte solution:
With A (0.0001mol-500mol), [A-A]
2+(TFSI)
2(0.01mol-1mol), solvent M (0.1mol-2000mol), ionic liquid C
+D
-(0-2000mol), additive G (0-500mol) and inorganic salts IS mix, stirring and dissolving obtains the described electrolyte solution of title.Described each component is recited in the table 5.
2. the assembling of battery and performance test thereof:
With prepared electrolyte with the carbon that adopts the preparation of hard carbon ball material to electrode, be assembled into DSSC through the light anode of dye sensitization, the photoelectrochemical behaviour test result of battery sees Table 5, and method of testing is with reference to method of testing used among the embodiment 1.
Embodiment 6
The preparation of 1 electrolyte solution:
With A (0.0001mol-500mol), [A-A]
2+(TFSI)
2(0.01mol-1mol), solvent M (0.1mol-2000mol), inorganic salts IS (0-500mol), additive G (0-500mol) and ionic liquid C
+D
-Mix, stirring and dissolving obtains the described electrolyte solution of title.Described each component is recited in the table 6.
2. the assembling of battery and performance test thereof:
With prepared electrolyte with the carbon that adopts the preparation of hard carbon ball material to electrode, be assembled into DSSC through the light anode of dye sensitization, the photoelectrochemical behaviour test result of battery sees Table 6, and method of testing is with reference to method of testing used among the embodiment 1.
Embodiment 7
1. the preparation of electrolyte solution:
With A (0.0001mol-500mol), [A-A]
2+(TFSI)
2(0.01mol-1mol), solvent M (0.1mol-2000mol), ionic liquid C
+D
-(0-2000mol), inorganic salts IS (0-500mol) and additive G mix, stirring and dissolving obtains the described electrolyte solution of title.Described each component is recited in the table 7.
2. the assembling of battery and performance test thereof:
With prepared electrolyte with the carbon that adopts the preparation of hard carbon ball material to electrode, be assembled into DSSC through the light anode of dye sensitization, the photoelectrochemical behaviour test result of battery sees Table 7, and method of testing is with reference to method of testing used among the embodiment 1.
Embodiment 8
1. preparation electrolyte solution:
With A (0.0001mol-500mol), [A-A]
2+(TFSI)
2(0.01mol-1mol), solvent M (0.1mol-2000mol), ionic liquid C
+D
-(0-2000mol), inorganic salts IS (0-500mol), additive G (0-500mol) mix, stirring and dissolving obtains the described electrolyte solution of title.Described each component is recited in the table 8.
2. the assembling of battery and performance test thereof:
With prepared electrolyte with the carbon that adopts the preparation of hard carbon ball material to electrode, be assembled into DSSC through the light anode of dye sensitization, the photoelectrochemical behaviour test result of battery sees Table 8, and method of testing is with reference to method of testing used among the embodiment 1.
Embodiment 9
1. the preparation of electrolyte solution:
With A (0.0001mol-500mol), [A-A]
2+(TFSI)
2(0.01mol-1mol), solvent M (0.1mol-2000mol) and other component mix, stirring and dissolving obtains the described electrolyte solution of title.Described each component is recited in the table 9.
2. the assembling of battery and performance test thereof:
Prepared electrolyte is assembled into DSSC with the carbon that adopts hard carbon ball and the Composite Preparation of conductive carbon black to the light anode of electrode, dye sensitization, the photoelectrochemical behaviour test result of battery sees Table 9, and method of testing is with reference to method of testing used among the embodiment 1.
Embodiment 10
1. the preparation of electrolyte solution:
With A (0.0001mol-500mol), [A-A]
2+(TFSI)
2(0.01mol-1mol), solvent M (0.1mol-2000mol), ionic liquid C
+D
-(0-2000mol) and other component mix, stirring and dissolving obtains the described electrolyte solution of title.Described each component is recited in the table 10.
2. the assembling of battery and performance test thereof:
Prepared electrolyte is assembled into DSSC with the carbon that adopts hard carbon ball and conductive carbon black Composite Preparation to the light anode of electrode, dye sensitization, the photoelectrochemical behaviour test result of battery sees Table 10, and method of testing is with reference to method of testing used among the embodiment 1.
Embodiment 11
1. the preparation of electrolyte solution:
With A (0.0001mol-500mol), [A-A]
2+(TFSI)
2(0.01mol-1mol), solvent M (0.1mol-2000mol), inorganic salts IS (0-500mol) and other component mix, stirring and dissolving obtains the described electrolyte solution of title.Described each component is recited in the table 11.
2. the assembling of battery and performance test thereof:
Prepared electrolyte is assembled into DSSC with the carbon that adopts hard carbon ball and conductive carbon black Composite Preparation to the light anode of electrode, dye sensitization, the photoelectrochemical behaviour test result of battery sees Table 11, and method of testing is with reference to method of testing used among the embodiment 1.
Embodiment 12
1. the preparation of electrolyte solution:
With A (0.0001mol-500mol), [A-A]
2+(TFSI)
2(0.01mol-1mol), solvent M (0.1mol-2000mol), additive G (0-500mol) and other component mix, stirring and dissolving obtains the described electrolyte solution of title.Described each component is recited in the table 12.
2. the assembling of battery and performance test thereof:
With prepared electrolyte with the carbon that adopts hard carbon ball and conductive carbon black Composite Preparation to electrode, be assembled into DSSC through the light anode of dye sensitization, the photoelectrochemical behaviour test result of battery sees Table 12, and method of testing is with reference to method of testing used among the embodiment 1.
Embodiment 13
1. the preparation of electrolyte solution:
With A (0.0001mol-500mol), [A-A]
2+(TFSI)
2(0.01mol-1mol), solvent M (0.1mol-2000mol), ionic liquid C
+D
-(0-2000mol), additive G (0-500mol) and inorganic salts mix, stirring and dissolving obtains the described electrolyte solution of title.Described each component is recited in the table 13.
2. the assembling of battery and performance test thereof:
With prepared electrolyte with the carbon that adopts hard carbon ball and conductive carbon black Composite Preparation to electrode, be assembled into DSSC through the light anode of dye sensitization, the photoelectrochemical behaviour test result of battery sees Table 13, and method of testing is with reference to method of testing used among the embodiment 1.
Embodiment 14
1. the preparation of electrolyte solution:
With A (0.0001mol-500mol), [A-A]
2+(TFSI)
2(0.01mol-1mol), solvent M (0.1mol-2000mol), inorganic salts IS (0-500mol), additive G (0-500mol) and ionic liquid C
+D
-Mix, stirring and dissolving obtains the described electrolyte solution of title.Described each component is recited in the table 14.
2. the assembling of battery and performance test thereof:
With prepared electrolyte with the carbon that adopts hard carbon ball and conductive carbon black Composite Preparation to electrode, be assembled into DSSC through the light anode of dye sensitization, the photoelectrochemical behaviour test result of battery sees Table 14, and method of testing is with reference to method of testing used among the embodiment 1.
Embodiment 15
1. the preparation of electrolyte solution:
With A (0.0001mol-500mol), [A-A]
2+(TFSI)
2(0.01mol-1mol), solvent M (0.1mol-2000mol), ionic liquid C
+D
-(0-2000mol), inorganic salts IS (0-500mol) and additive G mix, stirring and dissolving obtains the described electrolyte solution of title.Described each component is recited in the table 15.
2. the assembling of battery and performance test thereof:
With prepared electrolyte with the carbon that adopts hard carbon ball and conductive carbon black Composite Preparation to electrode, be assembled into DSSC through the light anode of dye sensitization, the photoelectrochemical behaviour test result of battery sees Table 15, and method of testing is with reference to method of testing used among the embodiment 1.
Embodiment 16
1. the preparation of electrolyte solution:
With A (0.0001mol-500mol), [A-A]
2+(TFSI)
2(0.01mol-1mol), solvent M (0.1mol-2000mol), ionic liquid C
+D
-(0-2000mol), inorganic salts IS (0-500mol), additive G (0-500mol) mix, stirring and dissolving obtains the described electrolyte solution of title.Each component is recited in the table 16.
2. the assembling of battery and performance test thereof:
With prepared electrolyte with the carbon that adopts hard carbon ball and conductive carbon black Composite Preparation to electrode, be assembled into DSSC through the light anode of dye sensitization, the photoelectrochemical behaviour test result of battery sees Table 16, and method of testing is with reference to method of testing used among the embodiment 1.
Can be according to the conversion efficiency of the measured battery of embodiment 1-embodiment 16 up to 5.94%, and the efficient of the non-oxide reduction electrolyte assembled battery of available technology adopting can reach 2.0% usually.Therefore, utilize the battery conversion efficiency of the electrolyte solution assembling contain oxidation-reduction pair of the present invention higher, and good stability, meet the development trend of DSSC, be fit to large-scale application.
Performance test
Stability test:
On the one hand, sheet metal is dialled in work such as aluminium flake, copper sheet be immersed in of the present invention containing in the non-iodine oxidation-reduction pair electrolyte solution, after two months, metallic luster still without any evidence of corrosion, illustrates that tentatively this type of electrolyte is very low to corrosion of metal; On the other hand, work such as aluminium flake, copper sheet are pulled out metal be immersed in DSSC the most frequent use contain I
3 -/ I
-In the electric right electrolyte, then react with interior in several seconds, promptly surface metal gloss disappears, has obvious corrosion pit.Can learn that freeze thaw stability of the present invention is higher.
Described the present invention in detail with reference to embodiment, to those skilled in the art, should be understood that, above-mentioned embodiment should not be understood that to limit scope of the present invention.Therefore, can make various changes and improvements to embodiment of the present invention without departing from the spirit and scope of the present invention.
Claims (15)
1. electrolyte solution that is used for DSSC, this electrolyte solution contains oxidation-reduction pair, and the general formula that this oxidation-reduction pair is formed is:
nA+([A-A]
2+B
2)
Wherein, A is the reduced form component in the oxidation-reduction pair, and its structure is as follows:
[A-A]
2+B
2Be the oxidized form component in the oxidation-reduction pair, its structure is as follows:
Equilibrium ion B is selected from halide ion, perchlorate, tetrafluoride boron ion, phosphorus hexafluoride ion, antimony fluoride ion, nitrate ion, two (fluorine sulphonyl) imines ion, two (trifluoromethyl sulphonyl) imines ion, (fluorine sulphonyl) (trifluoromethyl sulphonyl) imines ion and hexafluoro niobium ion;
N is A and [A-A]
2+B
2Mol ratio, 0.01≤n≤500.
2. electrolyte solution according to claim 1 is characterized in that, described halide ion is chloride ion and/or bromide ion.
3. electrolyte solution according to claim 1 is characterized in that described electrolyte solution also contains organic solvent M, and this organic solvent M is selected from nitrile; Alcohols; The ester class; Oxolane and composition thereof; M is described organic solvent M and [A-A]
2+B
2Mol ratio, and 10≤m≤2000.
4. electrolyte solution according to claim 3 is characterized in that, described nitrile is selected from acetonitrile, propionitrile, 3-methoxypropionitrile, 3-hydroxypropionitrile; Described alcohols is selected from methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols, octanol, ethylene glycol, glycerol, 1,2-propylene glycol, 1, ammediol; Described ester class is selected from dimethyl carbonate, diethyl carbonate, propene carbonate, methyl formate, Ethyl formate, butyl formate, ethyl acetate, methyl benzoate, ethyl benzoate, repefral, diethyl phthalate.
5. electrolyte solution according to claim 1 is characterized in that described electrolyte solution also contains ionic liquid C
+D
-, C wherein
+Be selected from imidazoles cation, pyrazoles cation, pyridines cation, piperidines cation, pyroles cation, indoles cation, carbazoles cation, quaternaries cation, trialkyl sulfonium cationoid and composition thereof; D
-Be selected from halide ion, tetrafluoride boron ion, phosphorus hexafluoride ion, antimony fluoride ion, perchlorate, nitrate ion, two (fluorine sulphonyl) imines ion, two (trifluoromethyl sulphonyl) imines ion, (fluorine sulphonyl) (trifluoromethyl sulphonyl) imines ion, hexafluoro niobium ion and composition thereof; X is described ionic liquid and [A-A]
2+B
2Mol ratio, and 0≤x≤2000.
6. electrolyte solution according to claim 5 is characterized in that, described halide ion is chloride ion and/or bromide ion.
7. electrolyte solution according to claim 1, it is characterized in that, described electrolyte solution also contains inorganic salts IS, these inorganic salts IS is selected from lithium salts, sodium salt, sylvite, quaternary ammonium salt and composition thereof, and the anion among these inorganic salts IS is selected from perchlorate, halide ion, tetrafluoride boron ion, phosphorus hexafluoride ion, antimony fluoride ion, nitrate ion, two (fluorine sulphonyl) imines ion, two (trifluoromethyl sulphonyl) imines ion, (fluorine sulphonyl) (trifluoromethyl sulphonyl) imines ion, hexafluoro niobium ion and composition thereof; Y is described inorganic salts IS and [A-A]
2+B
2Mol ratio, and 0≤y≤500.
8. electrolyte solution according to claim 7 is characterized in that, described halide ion is chloride ion and/or bromide ion.
9. electrolyte solution according to claim 1, it is characterized in that, described electrolyte solution also contains additive G, this additive G is selected from pyridine, the 2-picoline, the 3-picoline, the 4-picoline, the 2-ethylpyridine, 3-ethylpyridine, the 4-ethylpyridine, the 2-tert .-butylpyridine, the 3-tert .-butylpyridine, the 4-tert .-butylpyridine, 2-propyl group pyridine, 3-propyl group pyridine, 4-propyl group pyridine, 2-normal-butyl pyridine, 3-normal-butyl pyridine, 4-normal-butyl pyridine, the 2-pentyl pyridine, the 3-pentyl pyridine, the 4-pentyl pyridine, 2,4, the 6-trimethylpyridine, 2,3, the 5-trimethylpyridine, 2, the 4-lutidines, 2, the 5-lutidines, 3, the 5-lutidines, quinoline, isoquinolin and composition thereof; Z is described additive and [A-A]
2+B
2Mol ratio, and 0≤z≤500.
10. the application of each described electrolyte solution in the preparation DSSC in the claim 1 to 9.
11. DSSC that comprises each described electrolyte solution in the claim 1 to 9.
12. DSSC according to claim 11 is characterized in that, described DSSC comprises that also carbon is to electrode.
13. DSSC according to claim 12, it is characterized in that, described carbon comprises substrate and carbon film to electrode, described substrate is an Inorganic Non-metallic Materials, described carbon film is the compound of carbon ball or carbon ball and material with carbon element formation, and described material with carbon element is selected from conductive carbon black, carbon nano-tube, graphite and composition thereof.
14. DSSC according to claim 13 is characterized in that, described Inorganic Non-metallic Materials is an electro-conductive glass.
15. DSSC according to claim 11 is characterized in that, described battery also comprises TiO
2The light anode.
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| CN102651280B (en) * | 2011-02-25 | 2015-03-11 | 中国科学院化学研究所 | Ionic liquid electrolyte |
| CN102254688B (en) * | 2011-04-13 | 2012-12-26 | 清华大学 | Pyridine ionic liquid electrolyte as well as preparation method and application thereof |
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| JP6285263B2 (en) * | 2014-04-17 | 2018-02-28 | トヨタ自動車株式会社 | Electrolyte for fluoride ion battery and fluoride ion battery |
| JP6050290B2 (en) * | 2014-08-06 | 2016-12-21 | トヨタ自動車株式会社 | Electrolyte for fluoride ion battery and fluoride ion battery |
| CN104361997B (en) * | 2014-10-08 | 2018-04-17 | 浙江理工大学 | A kind of electrolyte solution for preparing DSC batteries |
| JP6880748B2 (en) * | 2017-01-10 | 2021-06-02 | 株式会社リコー | Photoelectric conversion element and solar cell |
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