CN102222571B - Addition agent for dye sensitized solar cell - Google Patents

Addition agent for dye sensitized solar cell Download PDF

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Publication number
CN102222571B
CN102222571B CN 201110078720 CN201110078720A CN102222571B CN 102222571 B CN102222571 B CN 102222571B CN 201110078720 CN201110078720 CN 201110078720 CN 201110078720 A CN201110078720 A CN 201110078720A CN 102222571 B CN102222571 B CN 102222571B
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obtains
electrolyte
mol
separates
add
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CN102222571A (en
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严锋
赵杰
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Suzhou University
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Suzhou University
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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
    • 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 discloses an addition agent for a dye sensitized solar cell. The addition agent is a pyridine ionic liquid addition agent, and the chemical structure general formula is as shown in the specification. The pyridine ionic liquid addition agent provided by the invention can be used for the addition agent of the electrolyte of the dye sensitized solar cell; the ionic liquid addition agent is simple in synthesis steps, is convenient to store, can not cause environmental pollution, and is difficult to volatilize and give out; and cell manufactured by adopting the ionic liquid addition agent has higher performances, and the stability of the cell is higher.

Description

The additive that is used for DSSC
Technical field
The invention belongs to field of dye-sensitized solar cells, relate to a kind of additive for DSSC.
Background technology
DSSC (DSC) is mainly formed by transparent conductive substrate, TiO 2 porous nano-crystal film, photosensitizer (dyestuff), electrolyte solution (containing oxidation-reduction pair) with to electrode, its basic principle is: dye sensitizing agent absorbs photon energy, produce electron-hole pair, electronics is injected into the titanium dioxide conduction band fast, be delivered to electrically-conductive backing plate through titanium deoxid film then, be delivered to electrode through external circuit again, get back to dyestuff ground state finally by oxidation-reduction pair, constitute cycle battery.In this process, electrolyte plays a part to transmit charge carrier, diffusion or charge carrier movement in electrolyte the electricity conversion that directly influenced DSC of oxidation-reduction pair in electrolyte.At present, according to electrolytical physical state difference, electrolyte can be divided into three kinds: liquid electrolyte, quasi-solid electrolyte and solid electrolyte.
Electrolyte is the especially core component of DSSC of solar cell, mainly plays redox couple, the good and bad solar battery efficiency that directly influences of its performance.And additive is electrolytical important component part, and the quality of its performance is to the open circuit voltage of battery, and short circuit current and dark current produce very important influence, and the effect of additive is by nitrogenous heterocycle and TiO 2In conjunction with coming negative its energy level that moves, and then strengthen the open circuit voltage of battery, antianode carries out passivation simultaneously, and block electrons compound improved battery efficiency.
In the prior art, the most frequently used and the most resultful additive is: and tert .-butylpyridine (TBP), N-tolimidazole (NMB), N-butyl benzimidazole (NMB) (referring to: people such as M. K. Nazeeruddin, J. Am. Chem. Soc., 1993,115,6382-6390; Kusama, H.; Arakawa, H. J. Photochem. Photobiol., A 2004,162; B. people such as Yu, Nature Mater, 2008,7,626).
Guanidine class ionic liquid also is used for strengthening battery performance, but mix use with other additive usually (referring to: Chem. Mater. 2004,16,2694-2696; J. Am. Chem. Soc., 2004,126,7164-7165; Nature Mater, 2008,7,626-630).
The patent No. is that to disclose a kind of be that initial reactant prepares dye-sensitized solar cell electrolyte additive with 2-methyl-4-nitropyridine N-O to the Chinese invention patent of 200810104933.X, the alkoxy grp of this compounds and pyridine ring constitute conjugation, make that nitrogen-atoms lone pair electrons charge density increases on the pyridine ring, it can with DSSC TiO 2Working electrode surface Ti 4 +Interionic forms strong coordination.Thereby this compounds can be used as the additive of dye-sensitized solar cell electrolyte, is used for improving the open circuit photovoltage of DSSC.
But, above-mentioned tert .-butylpyridine (TBP), N-tolimidazole (NMBI), N-butyl benzimidazole heterocycle additives such as (NBB) all are conventional organic substances, be assembled in the battery, because boiling point lower (190-250 ℃) can cause that volatilization is revealed and inflammability and the thermal instability of battery high-temperature operation, finally cause the unsteadiness of battery and battery performance to descend.
Summary of the invention
Goal of the invention of the present invention provides a kind of additive for DSSC.
To achieve the above object of the invention, the technical solution used in the present invention is: a kind of additive for DSSC, and described additive for DSSC is the benzimidazole ion liquid addictive, its chemical structure of general formula is:
Figure 596447DEST_PATH_IMAGE002
Or
Figure 2011100787206100002DEST_PATH_IMAGE003
, in the formula, n=0～11,
Figure 2011100787206100002DEST_PATH_IMAGE005
Be selected from:
Figure 893348DEST_PATH_IMAGE006
,
Figure 2011100787206100002DEST_PATH_IMAGE007
,
Figure 79610DEST_PATH_IMAGE008
Or
Figure 2011100787206100002DEST_PATH_IMAGE009
, wherein, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13Or R 14Independently be selected from respectively: the saturated alkyl of hydrogen or C1～C15, and R 5, R 6, R 7Be not hydrogen simultaneously;
Figure 19360DEST_PATH_IMAGE010
Be anion, be selected from: Cl -, Br -, I -, BF 4 -, PF 6 -, CF 3SO 3 -, C 2F 5SO 3 -, [N (SO 2CF 3) 2] -, [N (SO 2C 2F 5) 2] -, [N (SO 2C 3F 7) 2] -, SCN -, N (CN) 2 -, C (CN) 3 -, N (CF 3) -, SiF 6 -, B (CN) 4 -, CF 3COO -, C 2F 5COO -, NO 3 -, SO 4 -, ClO 4 -, or PO 4 -
In the optimized technical scheme, R is selected from: ,
Figure 787727DEST_PATH_IMAGE012
,
Figure 2011100787206100002DEST_PATH_IMAGE013
Or
Figure 125753DEST_PATH_IMAGE009
, wherein, R1 is selected from: the straight chain saturated alkane of hydrogen, C1～C15; R 5Be selected from: the straight chain saturated alkane of C1～C15; R 8Be selected from: the straight chain saturated alkane of hydrogen or C1～C15; R 14Be selected from: the straight chain saturated alkane of hydrogen or C1～C15; In the preferred technical scheme, R 1Be selected from: the straight chain saturated alkane of C1～C6; R 5Be selected from: the straight chain saturated alkane of C1～C6; R 8Be selected from: the straight chain saturated alkane of hydrogen or C1～C6; R 14Be selected from: the straight chain saturated alkane of C1～C6.
The preparation method of above-mentioned benzimidazole ion liquid addictive can reference: Rogers, R. D.; Seddon, K. R.; Volkov, S. In Green.Industrial Applications of Ionic Liquids; NATO Science. Series; Kluwer:Boston, 2002; Zhang Suojiang, Lv Xingmei etc. ionic liquid-from the basic research to the commercial Application. Beijing: Science Press, 2006, specifically can adopt any in the following method:
Method one:
When Y was Cl, Br, I a kind of, Y represented with X, represents halogen; The method for preparing the benzimidazole ion liquid addictive may further comprise the steps:
Step (1):
Figure 2011100787206100002DEST_PATH_IMAGE015
Step (2):
Figure 940257DEST_PATH_IMAGE016
N=0～11, X is a kind of of Cl, Br, I.
The a R of step (1) 0Excessive greatly dihalo alkane is fully reaction in acetonitrile, DMF, DMSO equal solvent, and column chromatography for separation obtains product;
Step (2) is under anhydrous condition, and slightly excessive benzimidazole is fully reaction under capacity conditions such as NaOH, KOH, NaH or KH, and the washing separation obtains final compound again.
When Y is BF 4 -, PF 6 -, CF 3SO 3 -, C 2F 5SO 3 -, [N (SO 2CF 3) 2] -, [N (SO 2C 2F 5) 2] -, [N (SO 2C 3F 7) 2] -, SCN -, N (CN) 2 -, C (CN) 3 -, N (CF 3) -, SiF 6 -, B (CN) 4 -, CF 3COO -, C 2F 5COO -, NO 3 -, SO 4 -, ClO 4 -, or PO 4 -The time, the method for preparing the benzimidazole ion liquid addictive may further comprise the steps:
Step (1):
Figure 496747DEST_PATH_IMAGE018
Or step (2):
Figure 447516DEST_PATH_IMAGE020
Step (3):
Figure 362251DEST_PATH_IMAGE022
The a R of step (1) 0Excessive greatly dihalo alkane is fully reaction in acetonitrile, DMF, DMSO equal solvent, and column chromatography for separation obtains product;
Step (2) is fully carried out anion exchange reaction in the solution of sodium salt, sylvite, lithium salts or the silver salt of the anion that will synthesize, separate to obtain product;
Step (3) is under anhydrous condition, and slightly excessive benzimidazole is fully reaction under capacity conditions such as NaOH, KOH, NaH or KH, and the washing separation obtains final compound again.The advantage of this method is that accessory substance is less, separates easily, and preparation cost is low.Shortcoming is in order to obtain the benzimidazole ionic liquid of various anion, and step 2 will be carried out various respective anionic exchanges earlier, and is more loaded down with trivial details.
Method two:
When Y was Cl, Br, I, Y represented with X, represented halogen; The method for preparing the benzimidazole ion liquid addictive may further comprise the steps:
Step (1):
Figure 683292DEST_PATH_IMAGE024
Step (2):
Figure 279359DEST_PATH_IMAGE026
Step (1) is under anhydrous condition, a benzimidazole and excessive greatly dihalo alkane be fully reaction under capacity conditions such as NaOH, KOH, NaH or KH, and post separates and obtains product.
When Y is BF 4 -, PF 6 -, CF 3SO 3 -, C 2F 5SO 3 -, [N (SO 2CF 3) 2] -, [N (SO 2C 2F 5) 2] -, [N (SO 2C 3F 7) 2] -, SCN -, N (CN) 2 -, C (CN) 3 -, N (CF 3) -, SiF 6 -, B (CN) 4 -, CF 3COO -, C 2F 5COO -, NO 3 -, SO 4 -, ClO 4 -, or PO 4 -The time, the method for preparing the benzimidazole ion liquid addictive may further comprise the steps:
Step (1):
Step (2):
Figure 2011100787206100002DEST_PATH_IMAGE029
Step (3):
Step (3) is fully to carry out anion exchange reaction in the solution of sodium salt, sylvite, lithium salts or the silver salt of the anion of the target product that finally needs, and separates obtaining end product.The advantage of this method be can be earlier the product of a large amount of synthesis steps two, conveniently utilize the anion exchange technology, carry out the preparation of all types of target product.Shortcoming is that the separation of product of step 1 is cumbersome, and accessory substance is more;
In the technique scheme, R 0Be selected from:
Figure 216277DEST_PATH_IMAGE032
,
Figure 809632DEST_PATH_IMAGE034
,
Figure 209390DEST_PATH_IMAGE036
Or
Above-mentioned preparation benzimidazole ionic liquid can be used as the additive of DSSC: according to molar concentration 0.05～1.0 mol/L, described benzimidazole ionic liquid is joined in liquid electrolyte, quasi-solid electrolyte or the solid electrolyte, in 30～100 ℃ of airtight thermal agitation 1～24 h that add, dissolving is even, and formation can be used for the electrolyte of DSSC.
Because technique scheme is used, the present invention compared with prior art has following advantage:
1. benzimidazole ionic liquid of the present invention can be used for the additive of dye-sensitized solar cell electrolyte; This ion liquid addictive, synthetic method is simple, and preparation easily is convenient to preserve, and can not be polluted environment, not volatile and leakage.
2. with the amount of substance concentration of ion liquid addictive of the present invention according to 0.05～1 mol/L, join in various present bibliographical informations organic solvent electrolyte, ionic liquid electrolyte, gel electrolyte, no iodine electrolyte and the solid electrolyte commonly used, replace the various additives that use at present, carry out cell preparation, encapsulation again; Under equal experiment condition, adopt ionic liquid of the present invention higher as the battery performance that additive makes, the stability of battery is higher.
Embodiment
Be further described still below in conjunction with the present invention of embodiment, be to be understood that the present invention is not limited to particular example described here and embodiment.The particular example that here comprises and the purpose of embodiment are to help those skilled in the art to put into practice the present invention.
Embodiment one:
Figure 735497DEST_PATH_IMAGE040
Preparation: get 0.82g
Figure 290850DEST_PATH_IMAGE042
, add 4g
Figure 448293DEST_PATH_IMAGE044
, under heating condition, react a couple of days, desolventizing, post separates, and obtains
Figure 8587DEST_PATH_IMAGE046
About 1.82g adds excessive slightly two fluoroform sulphonyl imido lithiums (LiTFSI) again, and reaction overnight is separated drying, obtains
Figure 143683DEST_PATH_IMAGE048
About 2.51g is again to wherein adding 0.7g
Figure 15693DEST_PATH_IMAGE050
, anhydrous and oxygen-free, fully reaction separates solvent and impurity under the excessive condition of KOH, obtains target product 2g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 9.05 (s, 1H), 8.22 (dd, 1H), 7.74 (s, 2H), 7.66 (s, 1H), 7.60 (t, 1H), 7.24 (m, 2H), 4.29 (m, 2H), 4.19 (m, 2H), 3.81 (s, 3H).
Embodiment two:
Figure DEST_PATH_IMAGE053
Preparation: get 0.82g
Figure 85149DEST_PATH_IMAGE042
, add 4g
Figure DEST_PATH_IMAGE055
, under heating condition, react a couple of days, desolventizing, post separates, and obtains
Figure DEST_PATH_IMAGE057
About 1.82g adds excessive slightly two fluoroform sulphonyl imido lithiums (LiTFSI) again, and reaction overnight is separated drying, obtains
Figure DEST_PATH_IMAGE059
About 1.85g is again to wherein adding 0.68g
Figure 625850DEST_PATH_IMAGE060
, anhydrous and oxygen-free, fully reaction separates solvent and impurity under the excessive condition of KOH, obtains target product
Figure DEST_PATH_IMAGE061
1.85g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 9.05 (s, 1H), 8.22 (dd, 1H), 7.74 (s, 2H), 7.66 (s, 1H), 7.60 (t, 1H), 7.24 (m, 2H) 4.28 (m, 2H), 4.18 (m, 2H), 3.82 (s, 3H), 1.1-1.9 (m, 16H).
Embodiment three:
Figure DEST_PATH_IMAGE063
Preparation: get 0.82g
Figure 394830DEST_PATH_IMAGE042
, add 4.5g , under heating condition, react a couple of days, desolventizing, post separates, and obtains
Figure DEST_PATH_IMAGE067
About 1.82g adds excessive slightly two fluoroform sulphonyl imido lithiums (LiTFSI) again, and reaction overnight is separated drying, obtains
Figure DEST_PATH_IMAGE069
About 1.85g is again to wherein adding 0.7g
Figure 806001DEST_PATH_IMAGE060
, anhydrous and oxygen-free, fully reaction separates solvent and impurity under the excessive condition of KOH, obtains target product
Figure 974420DEST_PATH_IMAGE070
1.80g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 9.05 (s, 1H), 8.22 (dd, 1H), 7.74 (s, 2H), 7.66 (s, 1H), 7.60 (t, 1H), 7.24 (m, 2H) 4.29 (m, 2H), 4.19 (m, 2H), 3.82 (s, 3H), 1.0-1.9 (m, 40H).
Embodiment four:
Figure 571624DEST_PATH_IMAGE072
Preparation: get 0.7g
Figure 888336DEST_PATH_IMAGE074
, add 4g
Figure 361036DEST_PATH_IMAGE055
, under heating condition, react a couple of days, desolventizing, post separates, and obtains
Figure 523027DEST_PATH_IMAGE076
About 1.77g adds excessive slightly two fluoroform sulphonyl imido lithiums (LiTFSI) again, and reaction overnight is separated drying, obtains About 1.9g is again to wherein adding 0.7g
Figure 564813DEST_PATH_IMAGE060
, anhydrous and oxygen-free, fully reaction separates solvent and impurity under the excessive condition of KOH, obtains target product
Figure DEST_PATH_IMAGE079
2.1g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 9.05 (s, 1H), 8.22 (dd, 1H), 7.74 (s, 2H), 7.66 (s, 1H), 7.60 (t, 1H), 7.24 (m, 2H) 4.28 (m, 2H), 4.18 (m, 2H), 3.82 (s, 3H), 1.1-1.9 (m, 16H).
Embodiment five:
Figure DEST_PATH_IMAGE081
Preparation: get 0.82g
Figure DEST_PATH_IMAGE083
, add 4g
Figure 600509DEST_PATH_IMAGE084
, under heating condition, react a couple of days, desolventizing, post separates, and obtains
Figure 523115DEST_PATH_IMAGE086
About 1.82g adds excessive slightly two fluoroform sulphonyl imido lithiums (LiTFSI) again, and reaction overnight is separated drying, obtains
Figure 829332DEST_PATH_IMAGE088
About 1.85g is again to wherein adding 0.68g
Figure 645103DEST_PATH_IMAGE050
, anhydrous and oxygen-free, fully reaction separates solvent and impurity under the excessive condition of KOH, obtains target product
Figure DEST_PATH_IMAGE089
1.85g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 9.05 (s, 1H), 8.22 (dd, 1H), 7.74 (s, 2H), 7.66 (s, 1H), 7.60 (t, 1H), 7.24 (m, 2H) 4.29 (m, 2H), 4.19 (m, 2H), 3.82 (d, 2H), 0.9-1.9 (dd, 25H).
Embodiment six:
Figure DEST_PATH_IMAGE091
Preparation: get 0.82g
Figure DEST_PATH_IMAGE093
, add 4g
Figure 558308DEST_PATH_IMAGE094
, under heating condition, react a couple of days, desolventizing, post separates, and obtains
Figure 16097DEST_PATH_IMAGE096
About 1.82g adds excessive slightly two fluoroform sulphonyl imido lithiums (LiTFSI) again, and reaction overnight is separated drying, obtains
Figure 770295DEST_PATH_IMAGE098
About 1.85g is again to wherein adding 0.68g , anhydrous and oxygen-free, fully reaction separates solvent and impurity under the excessive condition of KOH, obtains target product
Figure DEST_PATH_IMAGE099
1.85g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 9.05 (s, 1H), 8.22 (dd, 1H), 7.74 (s, 2H), 7.66 (s, 1H), 7.60 (t, 1H), 7.24 (m, 2H) 4.29 (m, 2H), 4.19 (m, 2H), 3.82 (d, 2H), 0.9-1.9 (dd, 45H).
Embodiment seven:
Figure DEST_PATH_IMAGE101
Preparation: get 0.82g
Figure 315992DEST_PATH_IMAGE042
, add 4.32g
Figure DEST_PATH_IMAGE103
, under heating condition, react a couple of days, desolventizing, post separates, and obtains
Figure DEST_PATH_IMAGE105
About 1.87g adds excessive slightly two fluoroform sulphonyl imido lithiums (LiTFSI) again, and reaction overnight is separated drying, obtains About 2.66g is again to wherein adding 0.7g
Figure 354968DEST_PATH_IMAGE060
, anhydrous and oxygen-free, fully reaction separates solvent and impurity under the excessive condition of KOH, obtains target product
Figure 933979DEST_PATH_IMAGE101
2.14g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 9.05 (s, 1H), 8.22 (dd, 1H), 7.74 (s, 2H), 7.66 (s, 1H), 7.60 (t, 1H), 7.24 (m, 2H) 4.25 (m, 2H), 3.32 (m, 2H), 4.18 (m, 2H), 3.82 (s, 3H).
Embodiment eight:
Figure DEST_PATH_IMAGE109
Preparation: get 0.82g
Figure 262192DEST_PATH_IMAGE042
, add 4.32g
Figure DEST_PATH_IMAGE111
, under heating condition, react a couple of days, desolventizing, post separates, and obtains About 1.85g adds excessive slightly two fluoroform sulphonyl imido lithiums (LiTFSI) again, and reaction overnight is separated drying, obtains
Figure DEST_PATH_IMAGE115
About 2.62g is again to wherein adding 0.7g
Figure 968898DEST_PATH_IMAGE060
, anhydrous and oxygen-free, fully reaction separates solvent and impurity under the excessive condition of KOH, obtains target product
Figure 283336DEST_PATH_IMAGE116
2.11g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 9.05 (s, 1H), 8.22 (dd, 1H), 7.74 (s, 2H), 7.66 (s, 1H), 7.60 (t, 1H), 7.24 (m, 2H) 4.25 (m, 2H), 3.0-3.6 (m, 10H), 4.18 (m, 2H), 3.82 (s, 3H).
Embodiment nine:
Figure 182765DEST_PATH_IMAGE118
Preparation: get 0.82g
Figure 603251DEST_PATH_IMAGE042
, add 4.50g
Figure 637066DEST_PATH_IMAGE120
, under heating condition, react a couple of days, desolventizing, post separates, and obtains
Figure 974769DEST_PATH_IMAGE122
About 1.98g adds excessive slightly two fluoroform sulphonyl imido lithiums (LiTFSI) again, and reaction overnight is separated drying, obtains
Figure 230170DEST_PATH_IMAGE124
About 2.72g is again to wherein adding 0.7g
Figure 189599DEST_PATH_IMAGE060
, anhydrous and oxygen-free, fully reaction separates solvent and impurity under the excessive condition of KOH, obtains target product
Figure DEST_PATH_IMAGE125
2.21g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 9.05 (s, 1H), 8.22 (dd, 1H), 7.74 (s, 2H), 7.66 (s, 1H), 7.60 (t, 1H), 7.24 (m, 2H) 4.25 (m, 2H), 3.0-3.6 (m, 22H), 4.18 (m, 2H), 3.82 (s, 3H).
Embodiment ten:
Preparation: get 0.82g
Figure 54918DEST_PATH_IMAGE042
, add 4.32g
Figure DEST_PATH_IMAGE129
, under heating condition, react a couple of days, desolventizing, post separates, and obtains
Figure DEST_PATH_IMAGE131
About 1.87g adds excessive slightly two fluoroform sulphonyl imido lithiums (LiTFSI) again, and reaction overnight is separated drying, obtains
Figure DEST_PATH_IMAGE133
1.94g, again to wherein adding 0.7g
Figure 599906DEST_PATH_IMAGE060
, anhydrous and oxygen-free, fully reaction separates solvent and impurity under the excessive condition of NaOH, obtains target product 1.71g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 9.05 (s, 1H), 8.22 (dd, 1H), 7.74 (s, 2H), 7.66 (s, 1H), 7.60 (t, 1H), 7.24 (m, 2H) 4.29 (m, 2H), 4.19 (m, 2H), 3.82 (s, 3H), 1.77 (dd, 4H).
Embodiment 11:
Figure 957255DEST_PATH_IMAGE136
Preparation: get 0.82g , add 4.32g
Figure 975994DEST_PATH_IMAGE129
, under heating condition, react a couple of days, desolventizing, post separates, and obtains
Figure 2725DEST_PATH_IMAGE138
About 1.87g adds excessive slightly Potassium Hexafluorophosphate (KPF again 6), reaction overnight is separated drying, obtains
Figure 781587DEST_PATH_IMAGE140
1.94g, again to wherein adding 0.7g
Figure 352989DEST_PATH_IMAGE060
, anhydrous and oxygen-free, fully reaction separates solvent and impurity under the excessive condition of NaOH, obtains target product
Figure DEST_PATH_IMAGE141
1.71g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 9.01 (s, 1H), 8.22 (dd, 1H), 7.74 (s, 2H), 7.66 (s, 1H), 7.60 (t, 1H), 7.24 (m, 2H) 4.29 (m, 2H), 4.19 (m, 2H), 3.82 (s, 3H), 1.77 (dd, 4H).
Embodiment 12
Figure DEST_PATH_IMAGE143
Preparation: get 0.82g
Figure 522938DEST_PATH_IMAGE042
, add 4.32g , under heating condition, react a couple of days, desolventizing, post separates, and obtains
Figure 88359DEST_PATH_IMAGE144
About 1.87g adds excessive slightly potassium tetrafluoroborate (KBF again 4), reaction 48h separates drying, obtains
Figure 195993DEST_PATH_IMAGE146
1.8g, again to wherein adding 0.7g
Figure 214371DEST_PATH_IMAGE060
, anhydrous and oxygen-free, fully reaction separates solvent and impurity under the excessive condition of NaOH, obtains target product
Figure 215694DEST_PATH_IMAGE143
1.64g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 9.02 (s, 1H), 8.22 (dd, 1H), 7.74 (s, 2H), 7.66 (s, 1H), 7.60 (t, 1H), 7.24 (m, 2H) 4.29 (m, 2H), 4.19 (m, 2H), 3.82 (s, 3H), 1.77 (dd, 4H).
Embodiment 13:
Figure 241419DEST_PATH_IMAGE148
Preparation: get 0.82g
Figure 134551DEST_PATH_IMAGE042
, add 4.32g
Figure 51560DEST_PATH_IMAGE129
, under heating condition, react a couple of days, desolventizing, post separates, and obtains
Figure DEST_PATH_IMAGE149
About 1.87g adds excessive slightly AgSCN again, and reaction 1h separates drying, obtains
Figure DEST_PATH_IMAGE151
1.81g, again to wherein adding 0.7g
Figure 693675DEST_PATH_IMAGE050
, anhydrous and oxygen-free, fully reaction separates solvent and impurity under the excessive condition of NaOH, obtains target product
Figure 982311DEST_PATH_IMAGE148
1.67g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 9.04 (s, 1H), 8.22 (dd, 1H), 7.74 (s, 2H), 7.66 (s, 1H), 7.60 (t, 1H), 7.24 (m, 2H) 4.29 (m, 2H), 4.19 (m, 2H), 3.82 (s, 3H), 1.77 (dd, 4H).
Embodiment 14:
Figure DEST_PATH_IMAGE153
Preparation: get 0.82g
Figure 133980DEST_PATH_IMAGE042
, add 4.32g
Figure 759740DEST_PATH_IMAGE129
, under heating condition, react a couple of days, desolventizing, post separates, and obtains
Figure 470076DEST_PATH_IMAGE149
About 1.87g adds excessive N aB (CN) slightly again 4, reacted 3 days, separate drying, obtain
Figure DEST_PATH_IMAGE155
1.80g, again to wherein adding 0.7g
Figure 902850DEST_PATH_IMAGE050
, anhydrous and oxygen-free, fully reaction separates solvent and impurity under the excessive condition of NaOH, obtains target product
Figure 816579DEST_PATH_IMAGE156
1.60g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 9.01 (s, 1H), 8.22 (dd, 1H), 7.74 (s, 2H), 7.66 (s, 1H), 7.60 (t, 1H), 7.24 (m, 2H) 4.29 (m, 2H), 4.19 (m, 2H), 3.82 (s, 3H), 1.77 (dd, 4H).
Embodiment 15:
Figure 932782DEST_PATH_IMAGE158
Preparation: get 0.82g
Figure 202352DEST_PATH_IMAGE042
, add 4.32g
Figure 130993DEST_PATH_IMAGE129
, under heating condition, react a couple of days, desolventizing, post separates, and obtains About 1.87g adds excessive slightly LiClO again 4, reacted 3 days, separate drying, obtain
Figure 585733DEST_PATH_IMAGE162
1.6g, again to wherein adding 0.7g
Figure 693497DEST_PATH_IMAGE050
, anhydrous and oxygen-free, fully reaction separates solvent and impurity under the excessive condition of NaOH, obtains target product
Figure DEST_PATH_IMAGE163
1.45g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 9.06 (s, 1H), 8.22 (dd, 1H), 7.74 (s, 2H), 7.66 (s, 1H), 7.60 (t, 1H), 7.24 (m, 2H) 4.29 (m, 2H), 4.19 (m, 2H), 3.82 (s, 3H), 1.77 (dd, 4H).
Embodiment 16:
Preparation: get 0.9g
Figure DEST_PATH_IMAGE167
, add 4g
Figure DEST_PATH_IMAGE169
, under heating condition, react a couple of days, desolventizing, post separates, and obtains
Figure DEST_PATH_IMAGE171
About 1.5g adds excessive slightly two fluoroform sulphonyl imido lithiums (LiTFSI) again, and reaction overnight is separated drying, obtains
Figure DEST_PATH_IMAGE173
About 1.8g is again to wherein adding 0.7g
Figure 371470DEST_PATH_IMAGE050
, anhydrous and oxygen-free, fully reaction separates solvent and impurity under the excessive condition of KOH, obtains target product 1.6g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 9.05 (s, 1H), 8.22 (dd, 1H), 7.74 (s, 2H), 7.66 (s, 1H), 7.60 (t, 1H), 7.24 (m, 2H) 4.29 (m, 2H), 4.19 (m, 2H), 0.95-1.9 (m, 43H).
Embodiment 17:
Figure 283243DEST_PATH_IMAGE176
Preparation: get 0.92g , add 4g
Figure 20352DEST_PATH_IMAGE180
, under heating condition, react a couple of days, desolventizing, post separates, and obtains
Figure 848500DEST_PATH_IMAGE182
About 1.45g adds excessive slightly two fluoroform sulphonyl imido lithiums (LiTFSI) again, and reaction overnight is separated drying, obtains
Figure 95548DEST_PATH_IMAGE184
About 1.52g is again to wherein adding 0.7g , anhydrous and oxygen-free, fully reaction separates solvent and impurity under the excessive condition of KOH, obtains target product 1.55g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 9.05 (s, 1H), 8.22 (dd, 1H), 7.74 (s, 2H), 7.66 (s, 1H), 7.60 (t, 1H), 7.24 (m, 2H) 4.25 (m, 2H), 4.16 (m, 2H), 0.9-1.9 (m, 108H).
Embodiment 18:
Figure 685427DEST_PATH_IMAGE186
Preparation: get 0.85g
Figure 340094DEST_PATH_IMAGE188
, add 4g
Figure 274027DEST_PATH_IMAGE055
, under heating condition, react a couple of days, desolventizing, post separates, and obtains
Figure 496061DEST_PATH_IMAGE190
About 1.82g adds excessive slightly two fluoroform sulphonyl imido lithiums (LiTFSI) again, and reaction overnight is separated drying, obtains About 1.85g is again to wherein adding 0.68g
Figure 687319DEST_PATH_IMAGE060
, anhydrous and oxygen-free, fully reaction separates solvent and impurity under the excessive condition of KOH, obtains target product
Figure DEST_PATH_IMAGE193
1.85g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 8.7 (s, 2H), 8.22 (dd, 1H), 7.74 (m, 3H), 7.66 (s, 1H), 7.60 (t, 1H), 7.40 (s, 2H), 7.24 (m, 2H), 4.29 (m, 2H), 4.19 (m, 2H), 1.0-1.79 (m, 16H).
Embodiment 19:
Preparation: get 0.95g
Figure DEST_PATH_IMAGE197
, add 4g
Figure DEST_PATH_IMAGE199
, under heating condition, react a couple of days, desolventizing, post separates, and obtains
Figure DEST_PATH_IMAGE201
About 1.85g adds excessive slightly two fluoroform sulphonyl imido lithiums (LiTFSI) again, and reaction overnight is separated drying, obtains
Figure DEST_PATH_IMAGE203
About 2g is again to wherein adding 0.72g
Figure 559499DEST_PATH_IMAGE050
, anhydrous and oxygen-free, fully reaction separates solvent and impurity under the excessive condition of KOH, obtains target product 2.1g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 8.7 (s, 2H), 8.22 (dd, 1H), 7.74 (s, 2H), 7.66 (s, 1H), 7.60 (t, 1H), 7.40 (s, 2H), 7.24 (m, 2H), 4.29 (m, 2H), 4.19 (m, 2H), 2.55 (d, 2H), 1.0-1.79 (m, 23H).
Embodiment 20:
Figure DEST_PATH_IMAGE205
Preparation: get 0.86g
Figure DEST_PATH_IMAGE207
, add 4g
Figure 226159DEST_PATH_IMAGE055
, under heating condition, react a couple of days, desolventizing, post separates, and obtains
Figure DEST_PATH_IMAGE209
About 1.72g adds excessive slightly two fluoroform sulphonyl imido lithiums (LiTFSI) again, and reaction overnight is separated drying, obtains
Figure DEST_PATH_IMAGE211
About 1.80g is again to wherein adding 0.7g
Figure 608248DEST_PATH_IMAGE060
, anhydrous and oxygen-free, fully reaction separates solvent and impurity under the excessive condition of KOH, obtains target product 1.82g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 8.22 (dd, 1H), 7.66 (s, 1H), 7.24 (m, 2H), 4.29 (m, 2H), 4.19 (m, 2H), 3.62 (s, 3H), 2.2-2.7 (m, 8H), 1.0-1.79 (m, 16H).
Embodiment 21:
Figure 83540DEST_PATH_IMAGE214
Preparation: get 0.88g
Figure 359407DEST_PATH_IMAGE216
, add 4g
Figure 853842DEST_PATH_IMAGE218
, under heating condition, react a couple of days, desolventizing, post separates, and obtains
Figure 839378DEST_PATH_IMAGE220
About 1.75g adds excessive slightly two fluoroform sulphonyl imido lithiums (LiTFSI) again, and reaction overnight is separated drying, obtains
Figure 378376DEST_PATH_IMAGE222
About 1.88g is again to wherein adding 0.71g
Figure 315108DEST_PATH_IMAGE050
, anhydrous and oxygen-free, fully reaction separates solvent and impurity under the excessive condition of KOH, obtains target product 1.99g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 8.22 (dd, 1H), 7.66 (s, 1H), 7.24 (m, 2H), 4.29 (m, 2H), 4.19 (m, 2H), 2.2-3.2 (m, 10H), 1.0-1.79 (m, 27H).
Embodiment 22:
Figure 859801DEST_PATH_IMAGE224
Preparation: get 1.18g
Figure 169036DEST_PATH_IMAGE226
, add
Figure 484742DEST_PATH_IMAGE228
10.8g anhydrous and oxygen-free under the excessive condition of KOH, fully reacts back desolventizing and solid impurity amount, post separates dry, obtains
Figure 215587DEST_PATH_IMAGE230
1.6g, again with 3g A couple of days is reacted in heating, and impurity obtains after separating
Figure DEST_PATH_IMAGE233
1.65g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 9.10 (s, 1H), 8.22 (dd, 1H), 7.74 (s, 2H), 7.66 (s, 1H), 7.60 (t, 1H), 7.24 (m, 2H) 4.29 (m, 2H), 4.19 (m, 2H), 3.82 (s, 3H).
Embodiment 23:
Figure DEST_PATH_IMAGE235
Preparation: get 1.18g
Figure 499860DEST_PATH_IMAGE226
, add
Figure DEST_PATH_IMAGE237
11g, anhydrous and oxygen-free under the excessive condition of KOH, fully reacts back desolventizing and solid impurity amount, and post separates dry, obtains
Figure DEST_PATH_IMAGE239
1.72g, again with 3.2g
Figure 581823DEST_PATH_IMAGE232
A couple of days is reacted in heating, and impurity obtains after separating
Figure 221752DEST_PATH_IMAGE235
1.8g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 9.08 (s, 1H), 8.22 (dd, 1H), 7.74 (s, 2H), 7.66 (s, 1H), 7.60 (t, 1H), 7.24 (m, 2H) 4.29 (m, 2H), 4.19 (m, 2H), 3.82 (s, 3H), 1.1-1.90 (dd, 20H).
Embodiment 24:
Figure DEST_PATH_IMAGE241
Preparation: get 1.18g
Figure 770807DEST_PATH_IMAGE226
, add
Figure 470779DEST_PATH_IMAGE237
12g, anhydrous and oxygen-free under the excessive condition of KOH, fully reacts back desolventizing and solid impurity amount, and post separates dry, obtains
Figure DEST_PATH_IMAGE243
1.75g, again with 3g
Figure 373793DEST_PATH_IMAGE232
A couple of days is reacted in heating, and impurity obtains after separating
Figure 692779DEST_PATH_IMAGE244
1.83g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 9.07 (s, 1H), 8.22 (dd, 1H), 7.74 (s, 2H), 7.66 (s, 1H), 7.60 (t, 1H), 7.24 (m, 2H) 4.29 (m, 2H), 4.19 (m, 2H), 3.82 (s, 3H), 1.0-1.9 (dd, 40H).
Embodiment 25:
Preparation: get 1.18g
Figure 498372DEST_PATH_IMAGE226
, add
Figure 977764DEST_PATH_IMAGE248
10g, anhydrous and oxygen-free under the excessive condition of KOH, fully reacts back desolventizing and solid impurity amount, and post separates dry, obtains
Figure 303703DEST_PATH_IMAGE250
1.65g, again with 3g A couple of days is reacted in heating, and impurity obtains after separating
Figure DEST_PATH_IMAGE251
1.71g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 9.06 (s, 1H), 8.22 (dd, 1H), 7.74 (s, 2H), 7.66 (s, 1H), 7.60 (t, 1H), 7.24 (m, 2H) 4.27 (m, 2H), 4.17 (m, 2H), 3.82 (s, 3H).
Embodiment 26:
Figure DEST_PATH_IMAGE253
Preparation: get 1.18g , add
Figure DEST_PATH_IMAGE255
11g, anhydrous and oxygen-free under the excessive condition of KOH, fully reacts back desolventizing and solid impurity amount, and post separates dry, obtains
Figure DEST_PATH_IMAGE257
1.74g, again with 3g
Figure 496198DEST_PATH_IMAGE232
A couple of days is reacted in heating, and impurity obtains after separating
Figure 251927DEST_PATH_IMAGE258
1.75g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 9.06 (s, 1H), 8.22 (dd, 1H), 7.74 (s, 2H), 7.66 (s, 1H), 7.60 (t, 1H), 7.24 (m, 2H) 4.27 (m, 2H), 4.17 (m, 2H), 3.82 (s, 3H), 3.42 (d, 10H).
Embodiment 27:
Preparation: get 1.18g , add
Figure 581561DEST_PATH_IMAGE262
12.5g anhydrous and oxygen-free under the excessive condition of KOH, fully reacts back desolventizing and solid impurity amount, post separates dry, obtains
Figure 967412DEST_PATH_IMAGE264
1.71g, again with 3g
Figure 527968DEST_PATH_IMAGE232
A couple of days is reacted in heating, and impurity obtains after separating
Figure DEST_PATH_IMAGE265
1.85g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 9.06 (s, 1H), 8.22 (dd, 1H), 7.74 (s, 2H), 7.66 (s, 1H), 7.60 (t, 1H), 7.24 (m, 2H) 4.27 (m, 2H), 4.17 (m, 2H), 3.82 (s, 3H), 3.3-3.6 (m, 20H).
Embodiment 28:
Figure DEST_PATH_IMAGE267
Preparation: get 1.18g
Figure 941239DEST_PATH_IMAGE226
, add
Figure DEST_PATH_IMAGE269
10.8g anhydrous and oxygen-free under the excessive condition of KOH, fully reacts back desolventizing and solid impurity amount, post separates dry, obtains 1.7g, again with 3g
Figure 711880DEST_PATH_IMAGE232
A couple of days is reacted in heating, and impurity obtains after separating
Figure DEST_PATH_IMAGE273
1.85g.Add 1.8g LiTFSI again, reaction overnight is separated drying, obtains
Figure 11010DEST_PATH_IMAGE267
2.51g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 9.03 (s, 1H), 8.22 (dd, 1H), 7.74 (s, 2H), 7.66 (s, 1H), 7.60 (t, 1H), 7.24 (m, 2H) 4.29 (m, 2H), 4.19 (m, 2H), 3.82 (s, 3H), 1.77 (dd, 4H).
Embodiment 29:
Figure DEST_PATH_IMAGE275
Preparation: get 1.18g , add
Figure 26556DEST_PATH_IMAGE269
10.8g anhydrous and oxygen-free under the excessive condition of KOH, fully reacts back desolventizing and solid impurity amount, post separates dry, obtains
Figure 222177DEST_PATH_IMAGE276
1.7g, again with 3g
Figure 90775DEST_PATH_IMAGE232
A couple of days is reacted in heating, and impurity obtains after separating
Figure 671930DEST_PATH_IMAGE273
1.85g.Add 1g AgSCN again, stirring reaction 2 hours separates drying, obtains 1.56g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 9.01 (s, 1H), 8.22 (dd, 1H), 7.74 (s, 2H), 7.66 (s, 1H), 7.60 (t, 1H), 7.24 (m, 2H) 4.29 (m, 2H), 4.19 (m, 2H), 3.82 (s, 3H), 1.77 (dd, 4H).
Embodiment 30:
Figure DEST_PATH_IMAGE279
Preparation: get 1.18g
Figure 754899DEST_PATH_IMAGE226
, add
Figure 172236DEST_PATH_IMAGE269
10.8g anhydrous and oxygen-free under the excessive condition of KOH, fully reacts back desolventizing and solid impurity amount, post separates dry, obtains
Figure 454313DEST_PATH_IMAGE280
1.7g (productive rate about 67%) is again with 3g A couple of days is reacted in heating, and impurity obtains after separating
Figure 114150DEST_PATH_IMAGE273
1.85g.Add 1.2g NaC (CN) again 3, stirring reaction 48 hours separates drying, obtains
Figure DEST_PATH_IMAGE281
1.52g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 9.0 (s, 1H), 8.22 (dd, 1H), 7.74 (s, 2H), 7.66 (s, 1H), 7.60 (t, 1H), 7.24 (m, 2H) 4.29 (m, 2H), 4.19 (m, 2H), 3.82 (s, 3H), 1.77 (dd, 4H).
Embodiment 31:
Figure DEST_PATH_IMAGE283
Preparation: get 1.18g
Figure 303604DEST_PATH_IMAGE226
, add 10.8g anhydrous and oxygen-free under the excessive condition of KOH, fully reacts back desolventizing and solid impurity amount, post separates dry, obtains
Figure 896183DEST_PATH_IMAGE271
1.7g (productive rate about 67%) is again with 3g
Figure 25682DEST_PATH_IMAGE232
A couple of days is reacted in heating, and impurity obtains after separating
Figure 135720DEST_PATH_IMAGE273
1.85g.Add 1.2g NaNO again 3, stirring reaction 48 hours separates drying, obtains
Figure 510332DEST_PATH_IMAGE284
1.32g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 9.06 (s, 1H), 8.22 (dd, 1H), 7.74 (s, 2H), 7.66 (s, 1H), 7.60 (t, 1H), 7.24 (m, 2H) 4.29 (m, 2H), 4.19 (m, 2H), 3.82 (s, 3H), 1.77 (dd, 4H).
Embodiment 32:
Figure 459266DEST_PATH_IMAGE286
Preparation: get 1.18g
Figure 323448DEST_PATH_IMAGE288
, add
Figure 917852DEST_PATH_IMAGE269
10.8g anhydrous and oxygen-free under the excessive condition of KOH, fully reacts back desolventizing and solid impurity amount, post separates dry, obtains
Figure 237101DEST_PATH_IMAGE276
1.7g, again with 3g
Figure 501860DEST_PATH_IMAGE232
A couple of days is reacted in heating, and impurity obtains after separating
Figure 707582DEST_PATH_IMAGE273
1.85g.Add 2g Li[N (SO again 2C 2F 5) 2], stirring reaction 10 hours separates drying, obtains 1.7g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 9.02 (s, 1H), 8.22 (dd, 1H), 7.74 (s, 2H), 7.66 (s, 1H), 7.60 (t, 1H), 7.24 (m, 2H) 4.29 (m, 2H), 4.19 (m, 2H), 3.82 (s, 3H), 1.77 (dd, 4H).
Embodiment 33:
Figure 608192DEST_PATH_IMAGE290
Preparation: get 1.18g
Figure 793448DEST_PATH_IMAGE226
, add
Figure 912713DEST_PATH_IMAGE292
10.8g anhydrous and oxygen-free under the excessive condition of KOH, fully reacts back desolventizing and solid impurity amount, post separates dry, obtains
Figure 178085DEST_PATH_IMAGE294
1.78g, again with 5g
Figure DEST_PATH_IMAGE295
A couple of days is reacted in heating, and impurity obtains after separating
Figure 422116DEST_PATH_IMAGE296
1.85g.Add 2g LiTFSI again, stirring reaction 10 hours separates drying, obtains
Figure 832236DEST_PATH_IMAGE290
2g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 9.05 (s, 1H), 8.22 (dd, 1H), 7.74 (s, 2H), 7.66 (s, 1H), 7.60 (t, 1H), 7.24 (m, 2H) 4.29 (m, 2H), 4.19 (m, 2H), 0.95-1.9 (m, 43H).
Embodiment 34:
Figure 789696DEST_PATH_IMAGE298
Preparation: get 1.18g , add
Figure 819280DEST_PATH_IMAGE292
10.8g anhydrous and oxygen-free under the excessive condition of KOH, fully reacts back desolventizing and solid impurity amount, post separates dry, obtains
Figure DEST_PATH_IMAGE299
1.78g, again with 5g A couple of days is reacted in heating, and impurity obtains after separating
Figure DEST_PATH_IMAGE303
1.85g.Add 2g LiTFSI again, stirring reaction 10 hours separates drying, obtains
Figure 457591DEST_PATH_IMAGE298
2g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 8.7 (s, 2H), 8.22 (dd, 1H), 7.74 (m, 3H), 7.66 (s, 1H), 7.60 (t, 1H), 7.40 (s, 2H), 7.24 (m, 2H), 4.29 (m, 2H), 4.19 (m, 2H), 1.0-1.79 (m, 16H).
Embodiment 35:
Figure DEST_PATH_IMAGE305
Preparation: get 1.18g
Figure 909038DEST_PATH_IMAGE226
, add
Figure 565148DEST_PATH_IMAGE292
10.8g anhydrous and oxygen-free under the excessive condition of KOH, fully reacts back desolventizing and solid impurity amount, post separates dry, obtains
Figure 439563DEST_PATH_IMAGE306
1.78g, again with 5g
Figure 973575DEST_PATH_IMAGE308
A couple of days is reacted in heating, and impurity obtains after separating
Figure 108890DEST_PATH_IMAGE310
1.9g.Add 2g LiTFSI again, stirring reaction 10 hours separates drying, obtains
Figure 349948DEST_PATH_IMAGE305
2.1g.Products therefrom is carried out nmr analysis, and the gained result is as follows: 1HNMR (400 MHz, DMSO-d 6): 8.22 (dd, 1H), 7.66 (s, 1H), 7.24 (m, 2H), 4.29 (m, 2H), 4.19 (m, 2H), 2.2-2.7 (m, 10H), 1.0-1.79 (m, 19H).
Embodiment 36:
With additive of the present invention
Figure 914921DEST_PATH_IMAGE312
According to 0.5 mol/L, join and contain LiI0.1 mol/L, 1,2-dimethyl-3-propyl imidazole iodized salt (DMPII) 0.6 mol/L, I 20.1 in the organic solvent electrolyte of the methoxypropionitrile of mol/L, obtain containing the electrolyte of dye sensitization additive of the present invention.Get this electrolyte of 0.05mL, drip at dye sensitization TiO 2Or the ZnO working electrode surface, and with the FTO glass of plating Pt as to being assembled into battery on the electrode cap, be used for the photoelectric properties test of DSSC.The results are shown in Table one.
Embodiment 37:
With additive of the present invention According to 0.5 mol/L, join and contain LiI0.1 mol/L, 1,2-dimethyl-3-propyl imidazole iodized salt (DMPII) 0.6 mol/L, I 20.1 in the organic solvent electrolyte of the methoxypropionitrile of mol/L, obtain containing the electrolyte of dye sensitization additive of the present invention.Get this electrolyte of 0.05mL, drip at dye sensitization TiO 2Or the ZnO working electrode surface, and with the FTO glass of plating Pt as to being assembled into battery on the electrode cap, be used for the photoelectric properties test of DSSC.The results are shown in Table one.
Comparing embodiment one:
Present existing 4-tertiary butyl pyridine (TBP) by 0.5 mol/L, is joined and contains LiI0.1 mol/L, 1,2-dimethyl-3-propyl imidazole iodized salt (DMPII) 0.6 mol/L, I 20.1 in the organic solvent electrolyte of the methoxypropionitrile of mol/L, obtain containing the electrolyte of dye sensitization additive of the present invention.Get this electrolyte of 0.05mL, drip at dye sensitization TiO 2Or the ZnO working electrode surface, and with the FTO glass of plating Pt as to being assembled into battery on the electrode cap, be used for the photoelectric properties test of DSSC.The results are shown in Table one.
Embodiment 38:
With additive of the present invention
Figure 662352DEST_PATH_IMAGE316
According to 0.45 mol/L, join and contain LiI 0.1 mol/L, I 20.1 in the mixed ionic liquid of the 1-of mol/L methyl-3-propyl imidazole iodized salt (PMII)/1-methyl-3-ethyl imidazol(e) rhodanate (EMINCS) (volume ratio 13:7), obtain containing the ionic liquid electrolyte of dye sensitization additive of the present invention.Get this electrolyte of 0.05mL, drip at dye sensitization TiO 2Or the ZnO working electrode surface, and with the FTO glass of plating Pt as to being assembled into battery on the electrode cap, be used for the photoelectric properties test of DSSC.The results are shown in Table one.
Embodiment 39:
With additive of the present invention
Figure 348679DEST_PATH_IMAGE314
According to 0.45 mol/L, join and contain LiI 0.1 mol/L, I 20.1 in the mixed ionic liquid of the 1-of mol/L methyl-3-propyl imidazole iodized salt (PMII)/1-methyl-3-ethyl imidazol(e) rhodanate (EMINCS) (volume ratio 13:7), obtain containing the ionic liquid electrolyte of dye sensitization additive of the present invention.Get this electrolyte of 0.05mL, drip at dye sensitization TiO 2Or the ZnO working electrode surface, and with the FTO glass of plating Pt as to being assembled into battery on the electrode cap, be used for the photoelectric properties test of DSSC.The results are shown in Table one.
Comparing embodiment two:
Existing N-butyl benzimidazole (NBB) according to 0.45 mol/L, is joined and contains LiI 0.1 mol/L, I 20.1 in the mixed ionic liquid of the 1-of mol/L methyl-3-propyl imidazole iodized salt (PMII)/1-methyl-3-ethyl imidazol(e) rhodanate (EMISCN) (volume ratio 13:7), obtain containing the ionic liquid electrolyte of dye sensitization additive of the present invention.Get this electrolyte of 0.05mL, drip at dye sensitization TiO 2Or the ZnO working electrode surface, and with the FTO glass of plating Pt as to being assembled into battery on the electrode cap, be used for the photoelectric properties test of DSSC.The results are shown in Table one.
Embodiment 40:
With of the present invention By 0.5 mol/L, join and contain
Figure DEST_PATH_IMAGE319
(McMT -) 0.2 mol/L,
Figure DEST_PATH_IMAGE321
(BMT) 0.2 mol/L, LiClO 40.05 mol/L, (Angew. Chem. Int. Ed. 2010,49 1-5.), obtains containing the I of dye sensitization additive of the present invention in the organic solvent electrolyte of acetonitrile (MeCN)/ethylene carbonate (EC) (volume ratio 6:4) 2-free electrolyte.Get this electrolyte of 0.05mL, drip at dye sensitization TiO 2Or the ZnO working electrode surface, and with the FTO glass of plating Pt as to being assembled into battery on the electrode cap, be used for the photoelectric properties test of DSSC.The results are shown in Table one.
Embodiment 41:
With of the present invention
Figure DEST_PATH_IMAGE323
By 0.5 mol/L, join and contain
Figure 512201DEST_PATH_IMAGE319
(McMT -) 0.2 mol/L, (BMT) 0.2 mol/L, LiClO 40.05 mol/L, (Angew. Chem. Int. Ed. 2010,49 1-5.), obtains containing the I of dye sensitization additive of the present invention in the organic solvent electrolyte of acetonitrile (MeCN)/ethylene carbonate (EC) (volume ratio 6:4) 2-free electrolyte.Get this electrolyte of 0.05mL, drip at dye sensitization TiO 2Or the ZnO working electrode surface, and with the FTO glass of plating Pt as to being assembled into battery on the electrode cap, be used for the photoelectric properties test of DSSC.The results are shown in Table one.
Comparing embodiment three:
Existing 4-tertiary butyl pyridine (TBP) by 0.5 mol/L, is joined and contains (McMT -) 0.2 mol/L, (BMT) 0.2 mol/L, LiClO 40.05 mol/L, (Angew. Chem. Int. Ed. 2010,49 1-5.), obtains containing the I of dye sensitization additive of the present invention in the organic solvent electrolyte of acetonitrile (MeCN)/ethylene carbonate (EC) (volume ratio 6:4) 2-free electrolyte.Get this electrolyte of 0.05mL, drip at dye sensitization TiO 2Or the ZnO working electrode surface, and with the FTO glass of plating Pt as to being assembled into battery on the electrode cap, be used for the photoelectric properties test of DSSC.The results are shown in Table one.
Embodiment 42:
With additive of the present invention
Figure DEST_PATH_IMAGE327
According to 0.5 mol/L, join and contain LiI 0.1 mol/L, 1,2-dimethyl-3-propyl imidazole iodized salt (DMPII) 0.6 mol/L, I 20.1 mol/L, and in the electrolyte of the methoxypropionitrile of the Kynoar-hexafluoropropylene of mass fraction 5% (P (VDF-HFP)) (Nature Materials, 2003,2,402-407.), obtain gel electrolyte.Get this electrolyte of 0.05mL, drip at dye sensitization TiO 2Or the ZnO working electrode surface, and with the FTO glass of plating Pt as to being assembled into battery on the electrode cap, be used for the photoelectric properties test of DSSC.The results are shown in Table one.
Embodiment 43:
With additive of the present invention
Figure DEST_PATH_IMAGE329
According to 0.5 mol/L, join and contain LiI 0.1 mol/L, 1,2-dimethyl-3-propyl imidazole iodized salt (DMPII) 0.6 mol/L, I 20.1 mol/L, and in the electrolyte of the methoxypropionitrile of the Kynoar-hexafluoropropylene of mass fraction 5% (P (VDF-HFP)) (Nature Materials, 2003,2,402-407.), obtain gel electrolyte.Get this electrolyte of 0.05mL, drip at dye sensitization TiO 2Or the ZnO working electrode surface, and with the FTO glass of plating Pt as to being assembled into battery on the electrode cap, be used for the photoelectric properties test of DSSC.The results are shown in Table one.
Comparing embodiment four:
Existing N-tolimidazole (NMBI) according to 0.5 mol/L, is joined and contains LiI 0.1 mol/L, 1,2-dimethyl-3-propyl imidazole iodized salt (DMPII) 0.6 mol/L, I 20.1 mol/L in the electrolyte of the methoxypropionitrile of the Kynoar-hexafluoropropylene of mass fraction 5% (P (VDF-HFP)), obtains gel electrolyte.Get this electrolyte of 0.05mL, drip at dye sensitization TiO 2Or the ZnO working electrode surface, and with the FTO glass of plating Pt as to being assembled into battery on the electrode cap, be used for the photoelectric properties test of DSSC.The results are shown in Table one.
Embodiment 44:
Get 0.05mL and contain additive of the present invention , two fluoroform sulfimide lithiums (LiTFSI), N (PhBr 3) SbCl 6, the chlorobenzene solution of spiro-MeOTAD drips at dye sensitization TiO 2Or the ZnO working electrode surface, after the spin coating, desolventizing is plated the gold electrode of the about 30nm of one deck more in the above and is formed battery, is used for the photoelectric properties test of DSSC.The results are shown in Table one.
Embodiment 45:
Get 0.05mL and contain additive of the present invention , two fluoroform sulfimide lithiums (LiTFSI), N (PhBr 3) SbCl 6, the chlorobenzene solution of spiro-MeOTAD drips at dye sensitization TiO 2Or the ZnO working electrode surface, after the spin coating, desolventizing is plated the gold electrode of the about 30nm of one deck more in the above and is formed battery, is used for the photoelectric properties test of DSSC.The results are shown in Table one.
Comparing embodiment five:
Get 0.05mL and contain 4-tertiary butyl pyridine (TBP), two fluoroform sulfimide lithiums (LiTFSI), N (PhBr 3) SbCl 6, the chlorobenzene solution of spiro-MeOTAD drips at dye sensitization TiO 2Or the ZnO working electrode surface, after the spin coating, desolventizing, the gold electrode that plates the about 30nm of one deck more in the above form battery (Adv. Mater.2005,17,813-815.), be used for the photoelectric properties test of DSSC.The results are shown in Table one.
Annotate: raw materials such as the benzimidazole that the present invention uses, imidazoles, methylimidazole, various pyridine, pyrrolidines, various tertiary amine, various alkali, salt are from commercially available; The synthetic reference literature of various alkyl imidazoles: Tetrahedron Letters, 2006,47,1575-1579.The synthetic reference literature of various alkyl pyrrolidines: J. Mater. Chem. 2010,20,3694-3702.
Table one
Figure DEST_PATH_IMAGE334
Annotate: test condition: room temperature environment, use the xenon lamp simulated solar irradiation, light intensity 100 mW/cm 2Under the condition, record battery (effective area 0.16cm 2).
Wherein, , expression is worked as battery and is had peak power output (P Max ) time, corresponding electric current and the product of voltage and the ratio of short circuit current and open circuit voltage product.Electricity conversion calculates and adopts following formula:
Figure DEST_PATH_IMAGE338

Claims (3)

1. additive that is used for DSSC, described additive for DSSC is the benzimidazole ion liquid addictive, it is characterized in that, described benzimidazole ion liquid addictive chemical structure of general formula is:
Figure 2011100787206100001DEST_PATH_IMAGE001
Or , in the formula, n=0～11,
Figure 2011100787206100001DEST_PATH_IMAGE003
Be selected from:
Figure 2011100787206100001DEST_PATH_IMAGE004
Or
Figure 2011100787206100001DEST_PATH_IMAGE005
, wherein, R 1, R 2, R 3, R 4Independently be selected from respectively: the saturated alkyl of hydrogen or C1～C15;
Figure DEST_PATH_IMAGE006
Be anion, be selected from: Cl -, Br -, I -, BF 4 -, PF 6 -, SCN -, B (CN) 4 -, NO 3 -Or ClO 4 -
2. according to the described additive for DSSC of claim 1, it is characterized in that,
Figure 99697DEST_PATH_IMAGE003
Be selected from:
Figure 2011100787206100001DEST_PATH_IMAGE007
, or , wherein, R1 is selected from: the straight chain saturated alkyl of hydrogen, C1～C15.
3. according to the described additive for DSSC of claim 2, it is characterized in that R 1Be selected from: the straight chain saturated alkyl of C1～C6.
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