CN110981829A - Preparation method of high-air-stability cathode interface layer - Google Patents

Preparation method of high-air-stability cathode interface layer Download PDF

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CN110981829A
CN110981829A CN201911290922.XA CN201911290922A CN110981829A CN 110981829 A CN110981829 A CN 110981829A CN 201911290922 A CN201911290922 A CN 201911290922A CN 110981829 A CN110981829 A CN 110981829A
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cathode interface
high air
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air stability
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周丹
徐镇田
杨飞
秦元成
谢宇
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Nanchang Hangkong University
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Abstract

The invention discloses a preparation method of a cathode interface layer with high air stability, which comprises the steps of firstly carrying out Suzuki coupling reaction on 2- (9, 9-bis (6-bromohexyl) -9H-fluorene) -4,4,5, 5-tetramethyl-oxyboronane hetero-pentalane and 4, 7-dibromo benzothiadiazole to prepare a fluorene and benzothiadiazole compound, then ionizing trimethylamine, and carrying out ion exchange on bis (trifluoromethane) sulfimide lithium or bis (pentafluoroethane) sulfimide lithium to obtain a final product. The side chain contains polar ion groups and F atoms, so that the polymer can form a dipole on an interface, reduce the interface potential barrier and improve the interface contact, can realize the processing of polar non-halogen solvents such as N, N-dimethylformamide, dimethyl sulfoxide and the like, and is environment-friendly. In addition, due to the existence of F atoms, the material is endowed with a hydrophobic function, the stability of the material in the air is improved, and the stability of the organic solar cell device in the air is improved.

Description

Preparation method of high-air-stability cathode interface layer
Technical Field
The invention relates to the technical field of cathode interfaces of organic solar cells, in particular to a preparation method of a cathode interface layer with high air stability.
Background
Global energy demand is increased year by year, renewable solar energy is effectively developed and utilized to inherit the national green development idea, the solar cell is the most direct mode for utilizing solar energy, the effective development and utilization of solar energy has important significance for the social and economic development of China, the current situations of energy shortage and environmental deterioration of China are changed, and the sustainable development of the social and economic of China is promoted. Therefore, improving the device efficiency of solar cells is a key to utilizing solar energy.
Although silicon-based solar cells have high photoelectric conversion efficiency, their further popularization and application are limited by the high cost. Compared with a silicon-based solar cell, the polymer solar cell can be prepared by a spin coating or printing method, so that the preparation cost can be effectively reduced, and meanwhile, the polymer solar cell also has the advantages of being capable of being prepared on a flexible substrate, easy to prepare in a large area, adjustable in material chemical property, green in energy source, free of environmental pollution and the like. With the continuous research and development of new high-efficiency active layer and interface layer materials and the continuous optimization of device structures, the efficiency of polymer solar cell devices exceeds 13%.
However, current device efficiencies still exist at a large distance from the need for commercial large area production. At present, the main obstacles for improving the efficiency of the polymer solar cell are two problems of poor stability of a device in air and interface barrier between an active layer and an electrode.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides synthesis of two kinds of micromolecule electrolyte cathode interface layers containing trifluoromethyl or pentafluoroethyl in terminal ions and application of the micromolecule electrolyte cathode interface layers in an organic solar cell. The conventional cathode interface layers are random or alternate water-soluble conjugated polymer electrolytes, fullerene derivatives, inorganic zinc oxide and the like, and the problem of poor interface barrier and stability of devices in air cannot be solved simultaneously by the cathode interface layers. The terminal ions of the two small molecular electrolytes designed by the invention contain trifluoromethyl or pentafluoroethyl, on one hand, the intramolecular or intermolecular C-F … H, C-F … S and other interactions caused by F atoms improve the planarity of the material, and the C-F bond induces to generate strong molecular dipoles and promote intermolecular dipole-dipole interactions, which is beneficial to tight pi-pi accumulation among chains and obtains higher crystallinity and favorable face-on molecular orientation, and the ordered face-on is beneficial to the transmission of carriers, thereby improving the efficiency of the device. And a dipole can be formed at the interface by utilizing the side-chain polar ion group, so that interface contact is improved, the interface potential barrier is reduced, and the transmission efficiency of carriers is improved. On the other hand, the trifluoromethyl group or pentafluoroethyl group contained in the terminal anion has a hydrophobic function. The stability of the device in humid air can be improved due to the presence of hydrophobic F atoms. Thirdly, the method comprises the following steps: because the tail end contains polar anions and cations, the micromolecule electrolyte can be dissolved in non-halogen solvents such as N, N-dimethylformamide, dimethyl sulfoxide and the like, is environment-friendly, and can be prevented from being mutually dissolved with an oil-soluble active layer to damage the appearance of the active layer.
The invention aims to provide a preparation method of a cathode interface layer with high air stability. The solar cell device prepared by the two cathode interface layers with high air stability is applied, and has better stability in the air.
The invention aims to provide a preparation method of a high-air-stability cathode interface layer with a structure shown in a formula I or a formula II.
Figure BDA0002319094970000021
Figure BDA0002319094970000031
The invention provides a preparation method of a high air stability cathode interface layer with a structure shown in a formula I or a formula II, which comprises the following steps: and (3) carrying out ion exchange on the compound 4 and bis (trifluoromethane) sulfonyl imide lithium or bis (pentafluoroethane) sulfonyl imide lithium in a nitrogen atmosphere to prepare the reaction specific step shown in the formula I or the formula II.
Figure BDA0002319094970000032
The invention also provides preparation of a solar cell device containing the high air stability cathode interface layer, which comprises an ITO glass layer, the high air stability cathode interface layer arranged on the ITO glass layer, an active layer arranged on the high air stability cathode interface layer, and MoO arranged on the active layer3Layer, set at the MoO3An Ag electrode layer on the layer.
The invention also provides preparation of a solar cell device containing the high air stability cathode interface layer, which comprises an ITO glass layer, a ZnO layer arranged on the ITO glass layer, a high air stability cathode interface layer arranged on the ZnO layer, an active layer arranged on the high air stability cathode interface layer, and MoO arranged on the active layer3Layer, set at the MoO3An Ag electrode layer on the layer.
The invention also provides a specific synthetic route of the high air stability small molecule electrolyte cathode interface layer FBFTFSI and FBFPFSI, and the reaction equation is as follows:
Figure BDA0002319094970000041
two preparation methods of high air stability cathode interface layer FBFTFSI and FBFPFSI are characterized by comprising the following specific preparation steps:
(1) synthesis of Compound 1: a dry 250mL round bottom flask was charged with 30mmol of 2-bromofluorene (7.35g), 150mmol of 1, 6-dibromohexane (36.29g), 0.1M NaOH (10mL), phase transfer catalyst tetra-n-butylammonium bromide 10mg, and 60mL of acetone. The reaction solution was refluxed and stirred at 80 ℃ overnight, acetone was spin-dried by a reduced-pressure rotary evaporator, excess 1, 6-dibromohexane was removed by reduced-pressure distillation, and the crude product was purified by extraction with n-hexane: purifying with silica gel column at ethyl acetate volume ratio of 2:1, and drying with anhydrous magnesium sulfate to obtain white solidThe product was obtained in 79% yield.1H NMR(400MHz,CDCl3),(ppm):7.54-7.58(t,3H),7.48-7.45(d,2H),7.44(s,2H),3.31-3.28(t,4H),1.95-1.90(t,4H),1.71-1.64(t,4H),1.24-1.17(t,4H),1.12-1.05(t,4H),0.63-0.55(t,4H).
(2) Synthesis of Compound 2: compound 1(5.68g,10mmol) was dissolved in dry THF (50mL), purged with nitrogen and the reaction cooled to-78 deg.C with liquid nitrogen. N-butyllithium (5.0mL,2.4M) was added dropwise to the stirred reaction mixture, and after the addition was complete, the temperature was maintained at-78 ℃ for one hour. Then (5.3mL,15mmol) 2-isopropyloxy-4, 4,5, 5-tetramethyl-1, 3, 2-oxaborolane was added to the reaction system, and the reaction mixture was stirred at room temperature for reaction overnight. After the reaction was completed, the reaction was quenched with water, extracted with dichloromethane and water, the organic layer was washed with saturated brine, and the organic layers were combined and dried over anhydrous magnesium sulfate. The crude product was used in the next reaction without purification by filtration and spin drying of the solvent, 83% yield.1H NMR(400MHz,CDCl3),(ppm):7.52-7.60(t,3H),7.43-7.47(d,2H),7.46(s,2H),3.30-3.29(t,4H),1.98(s,12H),1.94-1.90(t,4H),1.72-1.62(t,4H),1.23-1.17(t,4H),1.12-1.05(t,4H),0.63-0.55(t,4H).
(3) Synthesis of Compound 3: a100 mL polymer bottle was charged with 4, 7-dibromobenzothiadiazole (0.29g,1mmol), compound 2(3.70g,6mmol) and Pd (PPh)3)4(34mg,0.03mmol), and to the above polymer were added degassed toluene (15mL) and degassed 2M potassium carbonate (10mL), and the above reaction solution was evacuated and purged with nitrogen 3 times, followed by stirring at 110 ℃ for three days. After the reaction was completed, the reaction mixture was cooled to room temperature, the toluene solvent was removed by rotary evaporation under reduced pressure, and the obtained crude product was subjected to column chromatography using dichloromethane/n-hexane (2:1) to obtain a pale yellow solid with a yield of 81%.1H NMR(400MHz,CDCl3),(ppm):8.06-8.02(m,2H),7.54-7.58(t,6H),7.48-7.45(d,4H),7.44(s,4H),3.33-3.28(t,8H),1.96-1.91(t,8H),1.73-1.64(t,8H),1.27-1.17(t,8H),1.15-1.05(t,8H),0.66-0.54(t,8H).
(4) Synthesis of Compound 4:
300mg of Compound 3 were dissolved in 30mL THF at-78 deg.C, and an excess of trimethylamine solution (ca.13% inTHF, ca.2m)ol/L) (18.0mL) was added to the reaction. Stirring for 7 days at room temperature, once solid is precipitated, injecting 5mL of methanol to dissolve, supplementing 2.0mL of trimethylamine solution (ca.13% in THF, ca.2mol/L), after the reaction is finished, filtering the reaction solution, washing the obtained filter residue with dichloromethane for three times, dissolving the product in methanol, filtering out insoluble substances, dialyzing with a dialysis bag, removing impurities to obtain yellow solid, wherein the yield is as high as 93%.1H NMR(400MHz,CD3OD-d4),(ppm):8.06-8.01(m,2H),7.52-7.58(t,6H),7.48-7.45(d,4H),7.44(s,4H),3.36-3.07(t,32H),1.96-1.91(t,8H),1.73-1.64(t,8H),1.26-1.17(t,8H),1.17-1.05(t,8H),0.66-0.52(t,8H).
(5) Synthesis of high air stability cathode interface layer FBFTFSI: lithium bistrifluoromethanesulfonylimide (2.87g,10mmol) and 20mL deionized water were added to a 100mL nitrogen flask. Subsequently, 270mg of compound 4 was dissolved in 30mL of methanol and dropped dropwise into a nitrogen cylinder through a constant pressure dropping funnel. Stirring at room temperature for reaction for 3 days, after the reaction is finished, filtering, collecting filter residue, washing the obtained filter residue with deionized water and methanol, washing away redundant raw materials, and drying to obtain yellow solid with the yield of 92%.1H NMR(400MHz,DMSO-d6),(ppm):8.07-8.01(m,2H),7.54-7.60(t,6H),7.49-7.45(d,4H),7.44(s,4H),3.39-3.06(t,32H),1.97-1.91(t,8H),1.75-1.64(t,8H),1.27-1.17(t,8H),1.18-1.05(t,8H),0.67-0.52(t,8H).
(6) Synthesis of high air stability cathode interface layer FBFPFSI: lithium bis (pentafluoroethanesulfonyl) imide (3.00g,10mmol) and 20mL of deionized water were added under a nitrogen atmosphere in a 100mL nitrogen flask. Subsequently, 270mg of compound 4 was dissolved in 30mL of methanol and dropped dropwise into a nitrogen cylinder through a constant pressure dropping funnel. Stirring at room temperature for reaction for 3 days, after the reaction is finished, filtering, collecting filter residue, washing the obtained filter residue with deionized water and methanol, washing away redundant raw materials, and drying to obtain yellow solid with the yield of 91%.1H NMR(400MHz,DMSO-d6),(ppm):8.05-8.01(m,2H),7.52-7.59(t,6H),7.48-7.43(d,4H),7.42(s,4H),3.38-3.06(t,32H),1.96-1.91(t,8H),1.74-1.64(t,8H),1.28-1.17(t,8H),1.16-1.05(t,8H),0.66-0.52(t,8H).
Compared with the prior art, the method has strong innovation, and integrates the four advantages of small molecular compounds, C-F bond induced dipole self-assembly, polar side chains and high air stability. The method has the beneficial effects that two problems of poor stability of the device in air and interface potential barrier between the active layer and the electrode can be solved simultaneously. The method comprises the following specific steps: on the one hand, by introducing trifluoromethyl or pentafluoroethyl in the terminal anion, hydrophobic functions can be imparted to the material due to the presence of F atoms, and devices based on this material have better stability in humid air. Meanwhile, strong molecular dipoles generated by C-F bond induction can endow the material with better self-assembly performance, and a face-on arrangement structure favorable for carrier transmission is easily formed. Due to the existence of polar anions and cations of the branched chain, the processing of polar non-halogen solvents such as N, N-dimethylformamide, dimethyl sulfoxide and the like can be realized, and the pollution of the processing of the halogen solvents to the environment and the mutual dissolution of the halogen solvents and the active layer to destroy the appearance of the active layer are avoided; on the other hand, polar anions and cations of the branched chain can form dipoles on an interface, so that the interface potential barrier is reduced, the interface contact is improved, and the transmission efficiency of carriers is improved, thereby improving the photoelectric conversion efficiency of the device; thirdly, the method comprises the following steps: small molecules are introduced to serve as a cathode interface layer, so that the cathode interface layer is easy to process and purify and has a fixed structure. As shown in fig. 3, fig. 3a is the contact angle before the use of the high air stability cathode interface layer, fig. 3b is the contact angle after the use of the high air stability cathode interface layer FBFTFSI, and fig. 3c is the contact angle after the use of the high air stability cathode interface layer FBFPFSI. It can be seen that the contact angles increased from 46 ° to 82.5 ° and 94.5 ° after using the cathode interface layers FBFTFSI and FBFPFSI provided by the present invention, respectively, sufficiently illustrate that the hydrophobic properties and thus the stability in air can be greatly improved after using the interface layers FBFTFSI and FBFPFSI of the present invention. Furthermore, as can be seen from contact angle experiments, the more F atoms, the stronger the hydrophobicity, and the better the stability in air.
The current technology only uses random or alternate conjugated polymer electrolyte, fullerene derivative, inorganic zinc oxide and the like as cathode interface layers, and the cathode interface layers cannot solve the problems of large interface barrier between an active layer and an electrode and poor stability of a device in air. The four advantages of small molecular compounds, molecular dipole self-assembly induced by C-F bonds, dipole generation by polar side chains and high air stability cannot be integrated.
Drawings
Fig. 1 is a block diagram of two high air stability cathode interface layers FBFTFSI and FBFPFSI of the present invention.
FIG. 2 is a diagram of a device based on two high air stability cathode interfacial layers FBFTFSI and FBFPFSI of the present invention (a) replacing ZnO; (b) modifying ZnO.
FIG. 3 is a contact angle graph (a) reference ITO contact angle; (b) ITO/FBFTFSI contact angle; (c) ITO/FBFPFSI contact angles.
FIG. 4 is a graph of the reaction equations for two high air stability cathode interface layers FBFTFSI and FBFPFSI of the present invention.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
The reaction equation of the invention is shown in figure 4, and the specific reaction steps are as follows:
synthesizing high air stability cathode interface layer FBFTFSI and FBFPFSI:
(1) synthesis of Compound 1: a dry 250mL round bottom flask was charged with 2-bromofluorene (7.35g,30mmol), 1, 6-dibromohexane (36.29g,150mmol), 0.1M NaOH (10mL), phase transfer catalyst tetra-n-butylammonium bromide 10mg, and 60mL acetone. The reaction solution was refluxed and stirred at 80 ℃ overnight, acetone was spin-dried by a reduced-pressure rotary evaporator, excess 1, 6-dibromohexane was removed by reduced-pressure distillation, and the crude product was purified by extraction with n-hexane: the ethyl acetate was passed through a silica gel column at a volume ratio of 2:1 and purified, and dried over anhydrous magnesium sulfate to give the product as a white solid with a yield of 79%.1H NMR(400MHz,CDCl3),(ppm):7.54-7.58(t,3H),7.48-7.45(d,2H),7.44(s,2H),3.31-3.28(t,4H),1.95-1.90(t,4H),1.71-1.64(t,4H),1.24-1.17(t,4H),1.12-1.05(t,4H),0.63-0.55(t,4H).
(2) Synthesis of Compound 2: compound 1(5.68g,10mmol) was dissolved in dry THF (50mL), purged with nitrogen and the reaction cooled to-78 deg.C with liquid nitrogen. N-butyllithium (5.0mL,2.4M) was added dropwise to the stirred reaction mixture,after the dropwise addition, the temperature was maintained at-78 ℃ for one hour. Then (5.3mL,15mmol) 2-isopropyloxy-4, 4,5, 5-tetramethyl-1, 3, 2-oxaborolane was added to the reaction system, and the reaction mixture was stirred at room temperature for reaction overnight. After the reaction was completed, the reaction was quenched with water, extracted with dichloromethane and water, the organic layer was washed with saturated brine, and the organic layers were combined and dried over anhydrous magnesium sulfate. The crude product was used in the next reaction without purification by filtration and spin drying of the solvent, 83% yield.1H NMR(400MHz,CDCl3),(ppm):7.52-7.60(t,3H),7.43-7.47(d,2H),7.46(s,2H),3.30-3.29(t,4H),1.98(s,12H),1.94-1.90(t,4H),1.72-1.62(t,4H),1.23-1.17(t,4H),1.12-1.05(t,4H),0.63-0.55(t,4H).
(3) Synthesis of Compound 3: a100 mL polymer bottle was charged with 4, 7-dibromobenzothiadiazole (0.29g,1mmol), compound 2(3.70g,6mmol) and Pd (PPh)3)4(34mg,0.03mmol), and to the above polymer were added degassed toluene (15mL) and degassed 2M potassium carbonate (10mL), and the above reaction solution was evacuated and purged with nitrogen 3 times, followed by stirring at 110 ℃ for three days. After the reaction was completed, the reaction mixture was cooled to room temperature, the toluene solvent was removed by rotary evaporation under reduced pressure, and the obtained crude product was subjected to column chromatography using dichloromethane/n-hexane (2:1) to obtain a pale yellow solid with a yield of 81%.1H NMR(400MHz,CDCl3),(ppm):8.06-8.02(m,2H),7.54-7.58(t,6H),7.48-7.45(d,4H),7.44(s,4H),3.33-3.28(t,8H),1.96-1.91(t,8H),1.73-1.64(t,8H),1.27-1.17(t,8H),1.15-1.05(t,8H),0.66-0.54(t,8H).
(4) Synthesis of Compound 4:
300mg of Compound 3 was dissolved in 30mL of THF at-78 deg.C, and an excess amount of trimethylamine solution (ca.13% inTHF, ca.2mol/L) (18.0mL) was added to the reaction solution. Stirring for 7 days at room temperature, once solid is precipitated, injecting 5mL of methanol to dissolve, supplementing 2.0mL of trimethylamine solution (ca.13% in THF, ca.2mol/L), after the reaction is finished, filtering the reaction solution, washing the obtained filter residue with dichloromethane for three times, dissolving the product in methanol, filtering out insoluble substances, dialyzing with a dialysis bag, removing impurities to obtain yellow solid, wherein the yield is as high as 93%.1H NMR(400MHz,CD3OD-d4),(ppm):8.06-8.01(m,2H),7.52-7.58(t,6H),7.48-7.45(d,4H),7.44(s,4H),3.36-3.07(t,32H),1.96-1.91(t,8H),1.73-1.64(t,8H),1.26-1.17(t,8H),1.17-1.05(t,8H),0.66-0.52(t,8H).
(5) Synthesis of high air stability cathode interface layer FBFTFSI: lithium bistrifluoromethanesulfonylimide (2.87g,10mmol) and 20mL deionized water were added to a 100mL nitrogen flask. Subsequently, 270mg of compound 4 was dissolved in 30mL of methanol and dropped dropwise into a nitrogen cylinder through a constant pressure dropping funnel. Stirring at room temperature for reaction for 3 days, after the reaction is finished, filtering, collecting filter residue, washing the obtained filter residue with deionized water and methanol, washing away redundant raw materials, and drying to obtain yellow solid with the yield of 92%.1H NMR(400MHz,DMSO-d6),(ppm):8.07-8.01(m,2H),7.54-7.60(t,6H),7.49-7.45(d,4H),7.44(s,4H),3.39-3.06(t,32H),1.97-1.91(t,8H),1.75-1.64(t,8H),1.27-1.17(t,8H),1.18-1.05(t,8H),0.67-0.52(t,8H)。
(6) Synthesis of high air stability cathode interface layer FBFPFSI: lithium bis (pentafluoroethanesulfonyl) imide (3.00g,10mmol) and 20mL of deionized water were added under a nitrogen atmosphere in a 100mL nitrogen flask. Subsequently, 270mg of compound 4 was dissolved in 30mL of methanol and dropped dropwise into a nitrogen cylinder through a constant pressure dropping funnel. Stirring at room temperature for reaction for 3 days, after the reaction is finished, filtering, collecting filter residue, washing the obtained filter residue with deionized water and methanol, washing away redundant raw materials, and drying to obtain yellow solid with the yield of 91%.1H NMR(400MHz,DMSO-d6),(ppm):8.05-8.01(m,2H),7.52-7.59(t,6H),7.48-7.43(d,4H),7.42(s,4H),3.38-3.06(t,32H),1.96-1.91(t,8H),1.74-1.64(t,8H),1.28-1.17(t,8H),1.16-1.05(t,8H),0.66-0.52(t,8H).

Claims (6)

1. The high air stability cathode interface layer compound is characterized in that the high air stability cathode interface layer compound has a structure shown in formula I FBFTFSI or formula II FBFPFSI.
Figure FDA0002319094960000011
2. The preparation method of the two compounds of the cathode interface layer with high air stability is characterized in that the preparation method of the cathode interface layer with high air stability of the structure shown in the formula I or the formula II comprises the following steps:
(1) synthesis of high air stability cathode interface layer FBFTFSI: adding 2.87g of 10mmol of lithium bis (trifluoromethanesulfonyl) imide and 20mL of deionized water into a 100mL nitrogen bottle, dissolving 270mg of compound 4 into 30mL of methanol, dropwise adding the solution into the nitrogen bottle through a constant-pressure dropping funnel, stirring at room temperature for reaction for 3 days, filtering after the reaction is finished, collecting filter residues, washing the obtained filter residues with the deionized water and the methanol, washing away redundant raw materials, and drying to obtain yellow solid;
(2) synthesis of high air stability cathode interface layer FBFPFSI: under the nitrogen atmosphere, adding 3.00g of 10mmol of lithium bis (pentafluoroethane sulfonyl) imide and 20mL of deionized water into a 100mL nitrogen bottle, then dissolving 270mg of compound 4 into 30mL of methanol, dropwise adding the solution into the nitrogen bottle through a constant-pressure dropping funnel, stirring at room temperature for reaction for 3 days, filtering after the reaction is finished, collecting filter residues, washing the obtained filter residues with the deionized water and the methanol, washing away redundant raw materials, and drying to obtain a yellow solid.
3. The method for preparing a compound with high air stability on the cathode interface layer as claimed in claim 2, wherein the compound 4 has the following structure:
Figure FDA0002319094960000021
4. the method for preparing a compound of a high air stability cathode interface layer as claimed in claim 2, wherein the structure of the high air stability cathode interface layer is as follows:
Figure FDA0002319094960000022
5. the application of two compounds with high air stability cathode interface layers in the preparation of solar cell devices is characterized by comprising an ITO glass layer, the high air stability cathode interface layer arranged on the ITO glass layer, an active layer arranged on the high air stability cathode interface layer, a MoO3 layer arranged on the active layer and an Ag electrode layer arranged on the MoO3 layer.
6. The preparation of two solar cell devices containing high air stability cathode interface layers according to claim 5, wherein a ZnO layer is arranged on the ITO glass layer.
CN201911290922.XA 2019-12-16 2019-12-16 Preparation method of high-air-stability cathode interface layer Pending CN110981829A (en)

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