CN103606458B - A kind of oxidation-reduction pair and application thereof - Google Patents
A kind of oxidation-reduction pair and application thereof Download PDFInfo
- Publication number
- CN103606458B CN103606458B CN201310617143.2A CN201310617143A CN103606458B CN 103606458 B CN103606458 B CN 103606458B CN 201310617143 A CN201310617143 A CN 201310617143A CN 103606458 B CN103606458 B CN 103606458B
- Authority
- CN
- China
- Prior art keywords
- oxidation
- tempo
- reduction pair
- derivant
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention relates to a kind of oxidation-reduction pair, it is formed by containing iodide ion liquid and TEMPO derivant, and described TEMPO derivant is one or more the combination in the compound meeting following chemical general formula:、、、WithIn above-mentioned chemical general formula, a, b, c and d independently be the integer of 1 ~ 4, and Z is selected from Br, Cl, SCN, N (CN)2、C(CN)3、B(CN)4、BF4、PF6、CF3SO3、C2F5SO3、[N(SO2CF3)2]、ClO4And CF3One in COO. Oxidation-reduction pair of the present invention, by adding TEMPO derivant in containing iodide ion liquid, make this redox couple have a higher redox potential, and it is corrosion-free to metallic substrates, hardly pick up visible ray, it is adaptable to prepare dye-sensitized solar cell electrolyte.
Description
Technical field
The invention belongs to field of dye-sensitized solar cells, be specifically related to a kind of oxidation-reduction pair and application thereof.
Background technology
Oxidation-reduction pair (referred to as redox couple) is the core of solaode especially DSSC, the transmission being mainly used in DSSC electronics, the quality of its performance directly affects efficiency and the application of solaode.
At present, using in DSSC and study is I the most widely-/I3 -Oxidation-reduction pair. I-/I3 -Redox couple has the advantages such as fast and light induced electron the recombination velocity of electronic switching speeds is slow, but there is also the volatilization of the burn into iodine of the metallic substrates to current collector, absorb the shortcomings such as visible ray, and redox potential is on the low side, have impact on the large area of DSSC and commercial applications. Therefore, the redox couple with excellent properties is developed significant for the commercial applications of DSSC.
Along with going deep into that redox couple is studied, new redox couple is more and more diversified, mainly includes the coordination compound of the coordination compound of metal complex such as Co, the coordination compound of Fe, the coordination compound of Ni, Cu; Inorganic oxide reduces to such as Br3 -/Br-、SCN-/(SCN)2、SeCN-/(SeCN)2、S2-/Sn 2-Deng; Organic oxidation reduces to such as TEMPO(tetramethyl piperidine), benzoquinone, disulphide/mercaptan etc., wherein reduce based on the organic oxidation of TEMPO and the usefulness because of its excellence be widely studied. TEMPO is a kind of stable free radical, and the free radical centered by oxygen atom is subject to the sterically hindered protection of four methyl around and the conjugation of N-O group so that it is highly stable existence. But DSSC electricity conversion based on TEMPO redox couple is relatively low in prior art, it is impossible to meet the industrial requirement of solaode.
Summary of the invention
The invention aims to overcome the deficiencies in the prior art and a kind of oxidation-reduction pair having relatively high electrochemical electromotive force and can improving DSSC electricity conversion is provided.
For reaching above-mentioned purpose, the technical solution used in the present invention is: a kind of oxidation-reduction pair, and it is formed by containing iodide ion liquid and TEMPO derivant, and described TEMPO derivant is one or more the combination in the compound meeting following chemical general formula:
、、、With
In above-mentioned chemical general formula, a, b, c and d independently be the integer of 1 ~ 4, and Z is selected from Br, Cl, SCN, N (CN)2、C(CN)3、B(CN)4、BF4、PF6、CF3SO3、C2F5SO3、[N(SO2CF3)2]、ClO4And CF3One in COO.
Optimally, described is one or more the combination in the ionic liquid meeting following chemical general formula containing iodide ion liquid:
、、、、With
In above-mentioned chemical general formula, e is the integer of 1 ~ 4, and f is the integer of 1 ~ 6.
Further, the described mol ratio containing iodide ion liquid and TEMPO derivant is 1:0.1 ~ 1.
The present invention also provides for the application in the electrolyte preparing DSSC of a kind of redox couple.
Owing to technique scheme is used, the present invention compared with prior art has the advantage that oxidation-reduction pair of the present invention, by adding TEMPO derivant in containing iodide ion liquid, this oxidation-reduction pair is made to have higher redox potential, and it is corrosion-free to metallic substrates, hardly pick up visible ray, it is adaptable to prepare dye-sensitized solar cell electrolyte.
Detailed description of the invention
Oxidation-reduction pair of the present invention, is formed by containing iodide ion liquid and TEMPO derivant, and wherein TEMPO derivant is one or more the combination in the compound meeting following chemical general formula:
、、、With
In above-mentioned chemical general formula, a, b, c and d independently be the integer of 1 ~ 4, and Z is selected from Br, Cl, SCN, N (CN)2、C(CN)3、B(CN)4、BF4、PF6、CF3SO3、C2F5SO3、[N(SO2CF3)2]、ClO4And CF3One in COO. These TEMPO derivants due in the para-position of NO free radical containing the group such as hydroxyl or alkoxyl, itself and the redox couple containing iodide ion liquid composition have a high redox potential, and metallic substrates is corrosion-free, hardly pick up visible ray.
In order to improve the redox potential of redox couple further, and making TEMPO derivant and the liquid containing iodide ion have the good compatibility, described is one or more the combination in the ionic liquid meeting following chemical general formula containing iodide ion liquid:
、、、、With
In above-mentioned chemical general formula, e is the integer of 1 ~ 4, and f is the integer of 1 ~ 6.
In order to balance cost and redox potential numerical value, the mol ratio containing iodide ion liquid and TEMPO derivant is preferably 1:0.1 ~ 1.
Below in conjunction with embodiment, the invention will be further described:
Embodiment 1-17
It is configured to oxidation-reduction pair containing iodide ion liquid and TEMPO derivant by different mol ratio respectively by various, and this redox couple is carried out electro-chemical test: oxidation-reduction pair is dissolved in acetonitrile is formed and is 5mmol/L(mM every liter containing iodide ion strength of fluid) solution, and in this solution add LiClO4(as supporting electrolyte) makes its concentration be 0.1mol/L, is circulated volt-ampere test under three electrode conditions, and concrete outcome is listed in table 1.
Comparative example 1
WillAnd I2Oxidation-reduction pair is become (namely to automatically form I by 1:0.1 molar ratio-/I3 -Oxidoreduction), and this redox couple is carried out electro-chemical test, concrete outcome is listed in table 1.
From table 1 it follows that based on the oxidation-reduction pair of TEMPO derivant relative to I-/I3 -The redox potential of oxidation-reduction pair is significantly enhanced, and is promoted to more than 0.9V from original 0.39V, is conducive to the transmission of electronics in DSSC.
Component and chemical property in oxidation-reduction pair in table 1 embodiment 1-17 and comparative example 1.
| Oxidation-reduction pair | Mol ratio | Redox potential is (v) | |
| Comparative example 1 | , I2 | 1:0.1 | 0.39 |
| Embodiment 1 | , | 1:0.1 | 0.935 |
| Embodiment 2 | ,, | 1:0.1 | 0.936 |
| Embodiment 3 | , | 1:0.5 | 0.923 4 --> |
| Embodiment 4 | , | 1:0.5 | 0.931 |
| Embodiment 5 | , | 1:0.5 | 0.943 |
| Embodiment 6 | , | 1:0.5 | 0.937 |
| Embodiment 7 | , | 1:0.5 | 0.942 |
| Embodiment 8 | , | 1:0.1 | 0.935 5 --> |
| Embodiment 9 | , | 1:0.1 | 0.946 |
| Embodiment 10 | , | 1:0.1 | 0.932 |
| Embodiment 11 | , | 1:0.1 | 0.934 |
| Embodiment 12 | , | 1:0.3 | 0.926 |
| Embodiment 13 | , | 1:0.3 | 0.933 6 --> |
| Embodiment 14 | , | 1:0.3 | 0.943 |
| Embodiment 15 | , | 1:0.3 | 0.936 |
| Embodiment 16 | , | 1:0.3 | 0.942 |
| Embodiment 17 | , | 1:0.1 | 0.936 |
Embodiment 18
Prepare based on TEMPO derivant oxidation also to liquid electrolyte:
By 0.13g、0.008g, 0.006g oxidant Tetrafluoroboric acid nitrous additive (NOBF4) and 0.05g additive 4-tert .-butylpyridine (TBP) be dissolved in 5 milliliters of acetonitriles (ACN), obtain liquid electrolyte after stirring.
Assemble DSSC and measure performance:
With ultrasound wave, FTO electro-conductive glass is cleaned up, be dipped at 70 DEG C of 40mMTiCl4Aqueous solution keeps 30min, thus forming TiO one layer fine and close at FTO conductive glass surface2Film, dries after taking out FTO electro-conductive glass alcohol flushing subsequently naturally; With doctor blade technique, respectively P25 slurry, P400 slurry are applied to TiO2Film is formed the thickness respectively TiO of 8 μm and 3 μm again2Coating, heating is to 500 DEG C of calcinings, when FTO electro-conductive glass naturally cools to 80 DEG C, immerses 12h in dyestuff Z907 solution, takes out as light anode; Use H2PtCl6Solution is coated with a thin layer as to electrode at another block FTO electro-conductive glass; By thermoplastic film by light anode together with electrode is enclosed in, the battery structure of composition " sandwich " type, to having configured dripping several in aperture reserved on electrode, use vacuum filling technology is filled with, last thermoplastic film and microscope slide with 25 μ m-thick again seals, and DSSC is just made.
Surveying its redox potential is 0.92V, tests this DSSC electricity conversion, uses xenon lamp simulated solar irradiation, at 100mW/cm2Under, record battery (effective area 0.16cm2) photoelectric transformation efficiency is 7.33%.
Embodiment 19
Use the method identical with embodiment 1 to assemble DSSC, and test its photoelectric transformation efficiency. It is different in that the difference of the redox couple component in liquid electrolyte and content, in the present embodiment, 0.13g、0.025g, 0.006g oxidant Tetrafluoroboric acid nitrous additive (NOBF4) and 0.05g additive 4-tert .-butylpyridine (TBP) be dissolved in 5 milliliters of acetonitriles (ACN), obtain liquid electrolyte after stirring, surveying its redox potential is 0.931V, and cell photoelectric conversion efficiency is 7.76%.
Embodiment 20
Use the method identical with embodiment 1 to assemble DSSC, and test its photoelectric transformation efficiency. It is different in that the difference of the redox couple component in liquid electrolyte and content, in the present embodiment, 0.13g、0.035g, 0.006g oxidant Tetrafluoroboric acid nitrous additive (NOBF4) and 0.05g additive 4-tert .-butylpyridine (TBP) be dissolved in 5 milliliters of acetonitriles (ACN), liquid electrolyte is obtained after stirring, surveying its redox potential is 0.945V, and cell photoelectric conversion efficiency is 8.63%.
Above-described embodiment is only for illustrating technology design and the feature of the present invention; its object is to allow person skilled in the art will appreciate that present disclosure and to implement according to this; can not limit the scope of the invention with this; all equivalences made according to spirit of the invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (4)
1. an oxidation-reduction pair, it is characterised in that: it is formed by containing iodide ion liquid and TEMPO (tetramethyl piperidine) derivant, and described TEMPO derivant is one or more the combination in the compound meeting following chemical general formula:
、With
In above-mentioned chemical general formula, a, b, c and d independently be the integer of 1 ~ 4, and Z is selected from Br, Cl, SCN, N (CN)2、C(CN)3、B(CN)4、BF4、PF6、CF3SO3、C2F5SO3、[N(SO2CF3)2]、ClO4And CF3One in COO.
2. oxidation-reduction pair according to claim 1, it is characterised in that: described is one or more the combination in the ionic liquid meeting following chemical general formula containing iodide ion liquid:
、、、、With
In above-mentioned chemical general formula, e is the integer of 1 ~ 4, and f is the integer of 1 ~ 6.
3. oxidation-reduction pair according to claim 1, it is characterised in that: the described mol ratio containing iodide ion liquid and TEMPO derivant is 1:0.1 ~ 1.
4. in a claims 1 to 3 arbitrary described oxidation-reduction pair as the application of dye-sensitized solar cell electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310617143.2A CN103606458B (en) | 2013-11-29 | 2013-11-29 | A kind of oxidation-reduction pair and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310617143.2A CN103606458B (en) | 2013-11-29 | 2013-11-29 | A kind of oxidation-reduction pair and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103606458A CN103606458A (en) | 2014-02-26 |
| CN103606458B true CN103606458B (en) | 2016-06-15 |
Family
ID=50124674
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310617143.2A Expired - Fee Related CN103606458B (en) | 2013-11-29 | 2013-11-29 | A kind of oxidation-reduction pair and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103606458B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109574151B (en) * | 2018-11-22 | 2020-11-20 | 华南师范大学 | Method for continuous low-energy-consumption desalting by using material electrochemistry and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102568834A (en) * | 2011-11-14 | 2012-07-11 | 江苏德威新材料股份有限公司 | Electrolyte used for dye-sensitized solar cell and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101041931B1 (en) * | 2008-10-07 | 2011-06-16 | 한국과학기술연구원 | Dye-sensitized solar cell electrode using modified carbon nanotube grafted by living polymer and the fabrication method thereof |
-
2013
- 2013-11-29 CN CN201310617143.2A patent/CN103606458B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102568834A (en) * | 2011-11-14 | 2012-07-11 | 江苏德威新材料股份有限公司 | Electrolyte used for dye-sensitized solar cell and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103606458A (en) | 2014-02-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lin et al. | Mesoporous electrodeposited-CoS film as a counter electrode catalyst in dye-sensitized solar cells | |
| Hara et al. | Influence of electrolytes on the photovoltaic performance of organic dye-sensitized nanocrystalline TiO2 solar cells | |
| Ahmad et al. | A new generation of platinum and iodine free efficient dye-sensitized solar cells | |
| CN101630593B (en) | Electrolyte solution and application of same in dye-sensitized solar battery | |
| WO2014082704A1 (en) | Cobaltcomplex salts | |
| Wang et al. | Solidification of liquid electrolyte with imidazole polymers for quasi-solid-state dye-sensitized solar cells | |
| CN102712659A (en) | Electrolyte formulations | |
| Feng et al. | Single-crystal cobalt selenide nanobelt as a highly efficient cathode for stable quasi-solid-state dye sensitized solar cell | |
| JP5350851B2 (en) | Composition for photoelectric conversion element and photoelectric conversion element using the same | |
| CN116259810A (en) | Negative electrode electrolyte for alkaline all-iron flow battery and preparation method thereof | |
| CN103413682B (en) | A kind of quasi-solid electrolyte used for solar batteries based on Bis-imidazole ionic crystal | |
| KR20110095439A (en) | Ammonium imidazolium salt and electrolyte composition for dye-sensitized sollar cells containing the salt | |
| CN105753769B (en) | The small molecule hole transport material and its application in perovskite battery of carbazolyl-containing and low 4- tert .-butylpyridines dosage | |
| Nasr-Esfahani et al. | Fabrication and characterization of a new dye sensitized solar cell with a new Schiff base cobalt complex as a redox mediator | |
| Zhao et al. | Fine-tuning the coordination atoms of copper redox mediators: an effective strategy for boosting the photovoltage of dye-sensitized solar cells | |
| CN103606458B (en) | A kind of oxidation-reduction pair and application thereof | |
| CN103531364B (en) | A kind of hydrophobic solid electrolyte based on plastic crystals and application thereof | |
| JP5504744B2 (en) | Electrolyte for dye-sensitized solar cell and dye-sensitized solar cell | |
| JP2015141955A (en) | photoelectric conversion element | |
| CN103887069B (en) | A kind of electrolyte based on ionic liquid metal complex and preparation method thereof | |
| Ameen et al. | Effective metal loaded polyaniline nanofibers based potent counter electrode for solar energy conversion | |
| CN105390294A (en) | Quasi-solid electrolyte, based on bi-imidazole type ionic crystal, for solar cell | |
| CN101826396B (en) | Electrolyte composition and dye-sensitized solar battery using same | |
| WO2011019019A1 (en) | Electrolytic solution for dye-sensitized solar cells, and dye-sensitized solar cell | |
| CN103280319B (en) | Preparation method of transparent carbon electrode in dye sensitization solar battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160615 Termination date: 20181129 |