CN116239803B - Preparation of alcohol-phase conductive polymer by solvent exchange, method and application - Google Patents
Preparation of alcohol-phase conductive polymer by solvent exchange, method and application Download PDFInfo
- Publication number
- CN116239803B CN116239803B CN202310183746.XA CN202310183746A CN116239803B CN 116239803 B CN116239803 B CN 116239803B CN 202310183746 A CN202310183746 A CN 202310183746A CN 116239803 B CN116239803 B CN 116239803B
- Authority
- CN
- China
- Prior art keywords
- alcohol
- solvent
- conductive polymer
- semipermeable membrane
- phase conductive
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/095—Oxygen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2465/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Materials Engineering (AREA)
- Photovoltaic Devices (AREA)
Abstract
本发明涉及溶剂交换制备醇相导电聚合物、方法及应用，属于光电材料技术领域。将聚乙烯二氧噻吩与对阴离子的水溶液装入半透膜袋中，并将所述半透膜袋浸泡于第一醇溶剂中，使得水溶剂从半透膜袋中渗出，而第一醇溶剂则渗透进入半透膜袋中，从而实现溶剂交换；再向半透膜袋中加入第二醇溶剂和对阴离子，使所述聚乙烯二氧噻吩均匀分散同时改性，即得到所述醇相导电聚合物。本发明的醇相导电聚合物适用于不同结构的有机太阳能电池，该醇相导电聚合物能够有效地作为器件阳极使用而不需引入额外的阳极界面修饰层。本配方其他应用领域有防静电涂料、发光二极管、温差热电材料等。
The invention relates to the preparation of alcohol-phase conductive polymers by solvent exchange, methods and applications, and belongs to the technical field of optoelectronic materials. A solution of polyethylene dioxythiophene and anions is placed in a semipermeable membrane bag, and the semipermeable membrane bag is immersed in a first alcohol solvent, so that the aqueous solvent seeps out of the semipermeable membrane bag, while the first alcohol solvent penetrates into the semipermeable membrane bag, thereby achieving solvent exchange; a second alcohol solvent and anions are then added to the semipermeable membrane bag, so that the polyethylene dioxythiophene is uniformly dispersed and modified at the same time, thereby obtaining the alcohol-phase conductive polymer. The alcohol-phase conductive polymer of the invention is suitable for organic solar cells of different structures, and the alcohol-phase conductive polymer can be effectively used as a device anode without introducing an additional anode interface modification layer. Other application fields of this formula include antistatic coatings, light-emitting diodes, thermoelectric materials, etc.
Description
Technical Field
The invention belongs to the technical field of photoelectric materials, and particularly relates to a method for preparing an alcohol phase conductive polymer through solvent exchange, and an application thereof.
Background
In recent years, with the rapid development of photoelectric information technology, optoelectronic devices have become a research hotspot. In the photoelectric device, the most commonly used top electrode is a thermal evaporation metal electrode (gold, silver, aluminum, etc.), and the metal electrode needs to be thermally deposited under vacuum condition, which has high requirements on equipment and is difficult to realize mass production. In order to realize mass-printing production of optoelectronic devices, development of solution-processable electrodes has become a focus of attention. High performance solution processable electrodes need to possess high conductivity, low surface energy, and adjustable work function properties. At present, common electrode materials capable of being processed by solution include metal nanowires (gold, silver and the like), liquid metals (indium gallium alloy and the like), conductive polymers and the like. The metal nanowire has good photoelectric performance, but the film has high roughness, and is unfavorable for the preparation of a subsequent device functional layer. Liquid metals have high electrical conductivity but are difficult to wet on the surface of organic thin films.
The conductive polymer poly (3, 4-ethylenedioxythiophene) (PEDOT) has high conductivity, and can be dispersed in a solution by introducing counter anions such as polystyrene sulfonic acid (PSS), perfluorinated sulfonic acid Polymer (PFSA) and the like in the synthesis process, so that solution processing is realized. PEDOT has the characteristics of work function, adjustable light transmittance and small surface roughness for anion aqueous solution, and can be widely applied to the fields of photoelectric device collection, carrier injection, antistatic coating, thermoelectric materials and the like. PEDOT: PSS aqueous solutions were developed by Germany He Lishi (Heraeus) and Belgium Ikefa (Agfa) and the like and have been successfully commercialized. However, PEDOT/PSS aqueous dispersion has high surface energy, and is difficult to form a film on the surface of a hydrophobic film. In addition, PEDOT: PSS work function is low, and when the PEDOT: PSS electrode is used as an anode, an interface material is often required to modify the electrode. At present, an integrated printable electrode with good wettability and high work function is relatively lacking, and a preparation formula of an integrated alcohol phase electrode with simple development process and suitability for commercial mass production is needed.
In the invention patent with publication number CN114316223A, a perfluoro sulfonic acid polymer is disclosed as a novel conductive polyethylene dioxythiophene alcohol dispersion liquid for anions, and can be applied to the fields of hole transport layers, light-emitting diodes, antistatic coatings, electrochromic materials, thermoelectric materials, bioelectronics and the like of solar cells. The choice of anions in this patent is limited to one of the perfluorosulfonic acid polymers, which is not the most preferred choice for anions when preparing dispersions of PEDOT as other solvents such as butanol, dimethyl sulfoxide, etc., because of its better solubility in ethanol than in other solvents. In the invention, one PEDOT can be selected before dialysis exchange, and the second or more than two types of counter anions are introduced into the anion solution after dialysis exchange through post-treatment, so that the dispersibility of the PEDOT in different solvents is improved, and the conductivity and work function of the anion solution can be modified through post-treatment.
Disclosure of Invention
In order to overcome the defects and improvement requirements of the prior art, the invention provides a method for preparing an alcohol-phase conductive polymer by solvent exchange, which comprises the steps of filling an anion solution into a semipermeable membrane and soaking the anion solution in alcohol, realizing solvent exchange by utilizing the selective permeability of the semipermeable membrane, and obtaining a PEDOT alcohol solution with adjustable high electric conductivity work function through post-treatment (adding other anions and alcohol). The electrode prepared by the alcohol phase conductive polymer has good wettability on various interfaces, does not need to additionally increase an anode interface modification layer, and can be well applied to various photoelectric devices, thereby solving the problem of the defect of the high work function electrode which can be prepared in solution in the photoelectric device at the present stage.
According to a first aspect of the present invention there is provided a method of solvent exchange for preparing an alcohol phase conductive polymer comprising the steps of:
(1) Putting polyethylene dioxythiophene and an aqueous solution of a para-anion into a semipermeable membrane bag, and soaking the semipermeable membrane bag in a first alcohol solvent, wherein the polarity difference of the aqueous solvent and the first alcohol solvent causes the aqueous solvent to seep out of the semipermeable membrane bag, and the first alcohol solvent permeates into the semipermeable membrane bag, so that solvent exchange is realized;
(2) And adding a second solvent into the semipermeable membrane bag to uniformly disperse the polyethylene dioxythiophene, thereby obtaining the alcohol phase conductive polymer.
Preferably, the counter anion is at least one of polystyrene sulfonic acid, high-fluorine sulfonic acid ion polymer, sulfonated polyamide acid, sodium alkylbenzenesulfonate, fatty alcohol sulfate and sodium polystyrene sulfonate.
Preferably, in step (2), after the addition of the second solvent, the addition of other types of counter anions not present in the semipermeable membrane bag is also included.
Preferably, the ratio of the amount of polyethylene dioxythiophene to the amount of the substance to the anion in the aqueous solution is 1 (2.5-30).
Preferably, the first alcohol solvent described in step (1) and the second alcohol solvent described in step (2) are each independently selected from a C1-C10 aliphatic alcohol, a cycloaliphatic alcohol or an aromatic alcohol.
According to another aspect of the present invention, there is provided an alcohol phase conductive polymer prepared by any one of the methods.
According to another aspect of the invention there is provided the use of the alcohol phase conductive polymer for the preparation of a film.
According to another aspect of the invention, there is provided a film obtainable by said use.
Preferably, the film has a conductivity of 10 -4-103S cm-1 and a work function of 4.1 to 5.4eV.
According to another aspect of the invention there is provided the use of said film, in particular in solar cell electrodes, solar cell hole transport layers, antistatic films, thermoelectric devices or light emitting diodes.
In general, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
(1) The invention puts the conductive polyethylene dioxythiophene aqueous dispersion (PEDOT: para-anion) into the semipermeable membrane, and immerses the semipermeable membrane in alcohol solvent for permeation. Due to the polarity difference of the water solvent and the alcohol solvent, the speeds of the different solvents passing through the semipermeable membrane are different, so that the solvent exchange of PEDOT for anions is realized. In addition, by introducing two or more than two types of counter anions, the work function of the PEDOT-counter anionic alcohol solution can be adjusted, so that the PEDOT-counter anionic alcohol dispersion liquid with high work function and high conductivity can be realized. The electrode prepared by the alcohol phase conductive polymer has good wettability on various interfaces, does not need to additionally increase an anode interface modification layer, and can be well applied to various photoelectric devices, thereby solving the problem of the defect of high work function anode which can be prepared in solution in the photoelectric devices at the present stage.
(2) The obtained alcohol phase PEDOT electrode has good wettability and adjustable work function (4.1-5.4 eV), and the conductivity range of the film prepared by the prepared alcohol phase conductive polymer is 10 -4-103S cm-1. The alcohol phase conductive polymer is suitable for organic solar cells with different structures, and can be effectively used as a device anode without introducing an additional anode interface modification layer. Other application fields of the alcohol phase conductive polymer prepared by the invention include antistatic coating, light-emitting diode, thermoelectric material and the like.
(3) The solvent exchange strategy provided by the invention is used for preparing the alcohol phase conductive polymer formula, so that the problem that the traditional commercial PEDOT is not wetted when an anionic aqueous solution is coated on a hydrophobic surface is solved. The alcohol dispersion liquid has smaller surface tension, and can be coated and processed on any surface to prepare a uniform conductive film.
(4) The solvent exchange strategy provided by the invention has simple process, can realize solvent exchange by directly carrying out osmotic treatment on anions on the aqueous phase PEDOT, and can obtain conductive solutions of various solvents, and the preparation process has no dependence on large-scale equipment and vacuum degree.
(5) The alcohol phase conductive polymer is prepared by the solvent exchange strategy provided by the invention, and the permeation rate can be controlled by controlling the permeation time and the volume of the solvent to be exchanged so as to realize the regulation and control of the alcohol content of the conductive solution formula.
(6) Due to the addition of different anions, covalent bonds with high dipoles are introduced, and dipoles are formed on the surface of the film when the solution is formed into a film, so that the work function of PEDOT to the anion dispersion liquid is increased. In the preparation of the solar cell, the higher work function is beneficial to the upward band bending and ohmic contact between the electrode and the organic semiconductor active layer at the interface, so that efficient hole collection is realized.
(7) The alcohol phase conductive polymer formula prepared by the solvent exchange strategy provided by the invention has adjustable work function and conductivity, and is suitable for different types of solar cells, antistatic films, thermoelectric devices, light-emitting diodes and bioelectronic devices.
Drawings
FIG. 1 is a process of preparing an alcohol phase conductive polymer according to the solvent exchange strategy of the present invention.
FIG. 2 (a) is a graph showing transmittance of an alcohol phase polymer PEDOT: PSS electrode (e-PH 1000) film, and FIG. 2 (b) is a graph showing work function test of a film prepared from an alcohol phase polymer PEDOT: PSS solution.
FIG. 3 is a chart showing conductivity measurements of alcohol phase polymer PEDOT: PSS electrode (e-PH 1000) films.
Fig. 4 (a) is a schematic diagram of a trans-structured organic solar cell of the present invention (e-PH 1000 as anode), and fig. 4 (b) is a current density-voltage (J-V) curve of the corresponding device structure.
Fig. 5 (a) is a schematic view of the organic solar cell with the trans-structure of the present invention (e-4083 as a hole transport layer), and fig. 5 (b) is a current density-voltage (J-V) curve of the corresponding device structure.
Fig. 6 is a temperature difference-voltage curve of a thermoelectric device.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
FIG. 1 is a process of preparing an alcohol phase conductive polymer according to the solvent exchange strategy of the present invention. The invention relates to a method for preparing an alcohol phase conductive polymer by solvent exchange, which comprises the following steps:
(1) Putting polyethylene dioxythiophene and an aqueous solution of para anions into a semipermeable membrane bag, and soaking the semipermeable membrane bag into an alcohol solvent, wherein the polarity difference of the water solvent and the alcohol solvent causes the water solvent to seep out of the semipermeable membrane bag, and the alcohol solvent permeates into the semipermeable membrane bag, so that solvent exchange is realized;
(2) Adding alcohol into the semipermeable membrane bag, wherein the alcohol is the same as or different from the alcohol solvent in the step (1), so that the polyethylene dioxythiophene is uniformly dispersed, and the alcohol phase conductive polymer is obtained.
In some embodiments, the counter anion is at least one of polystyrene sulfonic acid (PSS), high-fluorosulfonic acid ionomer (PFSA), sulfonated polyamide acid (SPAA), sodium alkylbenzenesulfonate (LAS), fatty Alcohol Sulfate (FAS), and sodium polystyrene sulfonate (PSSNa)
In some embodiments, the semi-permeable membrane is a dialysis membrane made of regenerated cellulose, cellulose ester, PVDF, and MWCO cut-off of 100-50000 Da.
In some embodiments, the alcohol content can be achieved by controlling the permeation treatment time and the additional alcohol added, with a final alcohol content concentration of 5% to 99%.
In some embodiments, the commercial product PEDOT: PSS aqueous solution is selected from the group consisting of HSolar, pH500, 4083, pH1000, CH8000, etc.
In some embodiments, the conductivity of the thin film prepared by the alcohol phase conductive polymer formula is adjustable within 10 -4-103Scm-1, the work function is adjustable within 4.1-5.4eV, and the thin film can be prepared into a film by spin coating, knife coating, spraying and other processes, and can be used for preparing solar cell electrodes, solar cell hole transport layers, antistatic thin films, thermoelectric devices, light-emitting diodes and the like.
In some examples, conductive PEDOT-PSS ethanol dispersion [ NPG ASIA MATER 12,65 (2020) ] was prepared by ultrafiltration of commercially available pH1000 to remove water and adding ethanol as a dispersion, as compared to other forms of alcoholic PEDOT-PSS solutions. Due to the low dispersion concentration of the para-anionic PSS in the alcohol (below 5 mg/mL) in this formulation, it is difficult to obtain a stable PEDOT: PSS alcohol dispersion using PSS as the para-anion. The performance of the organic solar cell proves that the organic solar cell is not suitable for being applied to an anode of the organic solar cell.
Example 1
The technological process of preparing alcohol phase conducting polymer with solvent exchange strategy includes loading 6mL of water phase PEDOT to PSS (PH 1000) in the mass ratio of 1 to 2.5 into cellulose semipermeable membrane with molecular weight cut-off of 500Da and soaking in 500mL of alcohol. The polarities of ethanol and water are 0.654,1.000 respectively, and the water molecules with high polarity pass through the semipermeable membrane faster than the ethanol molecules. After 35mins permeation, 90% water molecules permeate from the dialysis bag into ethanol solution, then 6mL of ethanol and 5wt% of ethylene glycol secondary doping agent are added into PEDOT: PSS, cavitation effect is generated in the liquid by using strong ultrasound, solid particles in the liquid are completely dispersed by using an ultrasonic cell grinder for 2h, and the ethanol phase polymer PEDOT: PSS solution (e-PH 1000) is obtained.
The film is formed by a spin coating method, and the alcohol phase PEDOT: PSS solution prepared by dynamic spin coating is coated on clean glass, wherein the spin coating speed is 800 revolutions per minute. And after spin coating is finished, annealing is carried out for 3 minutes at a temperature of 100 ℃ and the alcohol solvent is volatilized, so that the thickness of the obtained film is 160nm, and the square resistance is 100 ohm/sq. Taking an alcohol phase PEDOT: PSS film with a thickness of 160nm as an example, the transmittance curve is shown in FIG. 2 (a), and the work function test is 4.9eV is shown in FIG. 2 (b).
Example 2
The process for preparing the alcohol phase conductive polymer by using the solvent exchange strategy can be suitable for other polar alcohol solvents, the common polar solvent table is shown in table 1, and n-butanol is taken as an example to realize solvent exchange to prepare an n-butanol phase PEDOT-PSS solution, namely, 3mL of aqueous phase PEDOT-PSS (PH 1000) is filled into a cellulose ester semipermeable membrane with the molecular weight cut-off of 500Da, and the cellulose ester semipermeable membrane is soaked in 300mL of n-butanol solution. Water molecules with high polarities of 0.586,1.000 are respectively n-butanol and water, and pass through the semipermeable membrane faster than n-butanol molecules. And (3) penetrating for 15 minutes until 95% of water molecules penetrate into n-butanol from a dialysis bag, adding 3mL of n-butanol into PEDOT-PSS, and treating for 2 hours by adopting an ultrasonic cell grinder to ensure that solid particles in the liquid are completely dispersed in an n-butanol solvent to obtain a polymer PEDOT-PSS solution of an n-butanol phase.
The film is processed by a spin coating method, and the obtained n-butanol phase PEDOT: PSS solution is dynamically spin coated on clean glass, wherein the spin coating speed is 800 revolutions per minute. And after spin coating, annealing at 100 ℃ for 3 minutes to wait for the volatilization of the alcohol solvent, wherein the thickness of the obtained film is 170nm.
TABLE 1 polarity table of alcohol solvents
Example 3
The process for preparing the alcohol phase conductive polymer by the solvent exchange strategy can be applied to other types of semipermeable membranes, wherein the types of the semipermeable membranes are dialysis membranes made of regenerated cellulose, cellulose ester and polyvinylidene fluoride (PVDF), and the molecular weight cut-off is varied from 100 Da to 50000 Da. Taking a cellulose ester semipermeable membrane with a molecular weight cutoff of 3000Da as an example, solvent exchange is realized to prepare an ethanol phase PEDOT/PSS solution, 6mL of water phase PEDOT/PSS (PH 1000) with a mass ratio of 1:2.5 is filled into the cellulose ester semipermeable membrane with a molecular weight cutoff of 3000Da, and the cellulose ester semipermeable membrane is soaked in 500mL of ethanol solution. And (3) penetrating 25 minutes until 88% of water molecules penetrate into ethanol from the dialysis bag, adding 6mL of ethanol into PEDOT (poly (styrene-co-acrylate)) PSS, and treating for 2 hours by adopting an ultrasonic cell grinder to ensure that solid particles in the liquid are completely dispersed in the ethanol solution to obtain an ethanol phase polymer PEDOT (poly (styrene-co-acrylate)) PSS solution.
The film is processed by a spin coating method, and the alcohol phase PEDOT: PSS solution prepared by dynamic spin coating is coated on clean glass, wherein the spin coating speed is 800 revolutions per minute. And after spin coating, annealing at 100 ℃ for 3 minutes to wait for the volatilization of the alcohol solvent, wherein the thickness of the obtained film is 180nm.
Example 4
The solvent exchange strategy of the invention prepares an alcohol phase conductive polymer formula, namely adding 4mg/mL of high fluorine sulfonate ion Polymer (PFSA) into 6mL of alcohol phase PEDOT: PSS (e-PH 1000) solution prepared in example 1 as stirring doping for 1h for anions. The PEDOT is processed into a film by using a spin coating method, and the PEDOT is prepared by dynamic spin coating on clean glass, wherein the spin coating speed is 800 revolutions per minute. And after spin coating, annealing at 100 ℃ for 3 minutes to wait for the volatilization of the alcohol solvent, wherein the thickness of the obtained film is 150nm. The work function test is 5.4eV, which is 4.9eV higher than the original work function of the aqueous phase PEDOT: PSS (PH 1000) film. The conductivity of the alcohol phase conductive polymer of this formulation was tested to be 5.3X10 2 S/cm. The conductivity was calculated using the 150nm film and the conductivity test is shown in FIG. 3.
Example 5
The organic solar cell with the trans-structure is prepared by the alcohol phase conductive polymer formula prepared by the solvent exchange strategy, does not need a hole transport layer, and can be directly used as an anode.
(1) Solvent exchange strategy an alcohol phase conductive polymer formulation was prepared example 4 was repeated with the same procedure described.
(2) Preparation of organic solar cell with trans-Structure the device structure of the trans-organic solar cell is shown in (a) of FIG. 4, and is glass/ITO/PEI-Zn/PM6: BTP-eC9: PC 71 BM/e-PH1000. Wherein, ITO glass is a bottom electrode, PEI-Zn is an electron transport layer, PM6 is BTP-eC9, PC 71 BM is a photoactive layer, and e-PH1000 is a hole transport layer and a top electrode; the preparation method comprises the following steps:
The cut and patterned transparent electrode Indium Tin Oxide (ITO) glass was ultrasonically cleaned with deionized water (detergent), acetone, and isopropyl alcohol sequentially for 15mins. Spin-coating PEI-Zn electron transport layer on the cleaned ITO glass sheet, heating at 3500 rpm and 200 ℃ for 20mins, spin-coating PM6:BTP-eC9:PC 71 BM active layer solution (total concentration is 18.7mg/mL, mass ratio is 1:1:0.2, solvent is chloroform) on the substrate, rotating at 1500 rpm, annealing at 100 ℃ for 10mins, doctor-blade coating e-PH1000 solution, doctor-blade coating substrate temperature at 70 ℃, doctor-blade height at 150 μm, and doctor-blade coating speed at 15mm/s. The film prepared by e-PH1000 has conductivity of 5.3X10 2 S/cm and work function of 5.4eV.
The current density-voltage of the organic solar cell device prepared using the method of this example is as in (b) of fig. 4, voltage represents voltage, current density represents current density, small area (0.04 cm 2) device open circuit voltage V OC =0.81V, current density J SC＝23.31mA/cm2, fill factor ff=0.74, efficiency pce=14.02%.
Example 6
The film prepared by the alcohol phase conductive polymer formula prepared by the solvent exchange strategy is directly used as a hole transport layer of a trans-organic solar cell.
(1) The technological process of preparing alcohol phase conducting polymer with solvent exchange strategy includes the steps of loading 6mL of water phase PEDOT to PSS (AI 4083) in the mass ratio of 1 to 6 into semi-transparent cellulose membrane with molecular weight cut-off of 500Da, and soaking in 500mL of isopropanol. The polarities of isopropanol and water are 0.546,1.000, respectively, and aqueous solutions with high polarities will preferentially permeate through the semipermeable membrane into the isopropanol solution. After 25 minutes of permeation, more than 93% of water molecules permeate into isopropanol from the dialysis bag, 6mL of isopropanol is added into PEDOT: PSS, and the cells are crushed for 2 hours to completely disperse in the isopropanol solution, so that an isopropanol-phase polymer PEDOT: PSS solution (e-4083) is obtained.
(2) The alcohol phase conductive polymer formula is prepared by a solvent exchange strategy, wherein e-4083 solution prepared by dynamic spin coating is coated on clean glass, and the spin coating speed is 3000 r/min. And after spin coating, annealing at 100 ℃ for 2 minutes to wait for the volatilization of the alcohol solvent, wherein the thickness of the obtained film is 40nm. The work function was 5.0eV and the conductivity was 4.0X10 -3 S/cm.
(3) Preparation of organic solar cell with trans-structure the device structure of the trans-organic solar cell is shown in (a) of FIG. 5, and is glass/ITO/PEI-Zn/PM6:Y6/e-4083/Ag. Wherein, ITO glass is a cathode layer, PEI-Zn is an electron transport layer, PM6:Y6 is a photoactive layer, e-4083 is a hole transport layer, and Ag is an anode layer. The preparation method comprises the following steps:
And sequentially ultrasonically cleaning the cut transparent electrode Indium Tin Oxide (ITO) glass with deionized water (detergent), acetone and isopropanol for 15 min. PEI-Zn electron transport layer solution was spin-coated on the cleaned ITO glass flake at 3500 rpm, followed by annealing at 150℃for 15mins. Spin-coating PM6:Y6 solution (total concentration is 17.8mg/ml, mass ratio is 1:1.2, solvent is chloroform) on the substrate, annealing at 100deg.C for 10min at 2500 rpm, spin-coating e-4083,3000 rpm on the active layer, and finally transferring the device into evaporation chamber, evaporating 70nm silver electrode under vacuum pressure of 2.6X10 -7 Torr.
The current density-voltage of the organic solar cell prepared using the method of this example is as shown in (b) of fig. 5, voltage represents voltage, current density represents current density, open circuit voltage V OC =0.82V, current density J SC＝25.86mA/cm2, fill factor ff=0.72, and efficiency pce=15.27%.
Example 7
The invention relates to a method for preparing an antistatic coating by a film prepared from an alcohol phase conductive polymer by a solvent exchange strategy, which comprises the following steps:
(1) The procedure for preparing an alcohol phase conductive polymer according to the solvent exchange strategy of the present invention is repeated for example 4 in the same manner as described. The conductivity of the film prepared from the synthesized e-4083 was 4.0X10 -3 S/cm.
(2) The antistatic coating is prepared through ultrasonic cleaning glass of 2.5 x 7.5cm 2 with deionized water, acetone and isopropanol in turn for 15: 15femins. Clean glass is placed on a doctor blade coating table with the substrate temperature of 50 ℃, 50 mu L of alcohol phase conductive polymer is taken, the slit height is set to be 100 mu m, the doctor blade coating speed is 15mm/s, the positive and negative alternate doctor blade coating is carried out for 1 to 30 times under the doctor blade coating condition, the film thickness of a film obtained by the doctor blade coating is adjustable between 20 nm and 10,000nm, and the sheet resistance is adjustable between 10 7-1010 omega.
Example 8
The thin film prepared by the alcohol phase conductive polymer formula prepared by the solvent exchange strategy of the invention adopts a spin coating mode to prepare a thermoelectric device, and the method is as follows:
(1) Synthesis of alcohol phase conductive Polymer PEDOT: PSS solution example 1 was repeated in the same procedure as described, and the synthesized e-PH1000 solution produced a film having a conductivity of 6.3X10 2 S/cm.
(2) The specific preparation process of the thermoelectric device comprises the step of sequentially ultrasonically cleaning glass with deionized water (detergent), acetone and isopropanol for 15min, wherein the glass is 2.5X5cm 2. E-PH1000 solution was spin-coated on the cleaned glass sheet at 800 rpm and heated on a 100℃hot plate for 10 minutes after spin-coating was completed. Silver paste with the smearing area of 2.5 multiplied by 0.2cm 2 at the two ends of the film is led out as an electrode.
The thermoelectric device temperature difference-voltage curve prepared by the method is shown in fig. 6, and the seebeck coefficient of the thermoelectric device is 28.63 mu V/K by fitting the curve.
Example 9
According to the comparative example of the method for preparing the alcohol phase conductive polymer by solvent exchange, 6mL of aqueous phase PEDOT-PSS (PH 1000) with the mass ratio of 1:2.5 is placed in an ultrafiltration container, a vacuum pump is used for extracting the solvent from the aqueous phase PEDOT-PSS (PH 1000), a semipermeable membrane with the molecular weight of 10000Da is used for sealing the ultrafiltration container, the solvent is removed by utilizing the pressure difference between two sides of the membrane, and 6mL of ethanol is added into the solvent to prepare the PEDOT-PSS ethanol dispersion, the PEDOT has obviously larger aggregation, and larger solid particles in the ethanol solution are difficult to eliminate even though an ultrasonic cell grinder is also used for 2 hours. And then, adding Ethylene Glycol (EG) to dope to improve conductivity, and preparing the organic solar cell with a trans-structure by using the prepared solution, wherein the device structure of the trans-organic solar cell is glass/ITO/PEI-Zn/PM6:BTP-eC9:PC 71 BM/PEDOT:PSS. Wherein, ITO glass is the bottom electrode, PEI-Zn is as electron transport layer, PM6: BTP-eC9 PC 71 BM is used as a photoactive layer, PEDOT PSS is used as a hole transport layer and a top electrode, and the preparation method is as follows:
The cut and patterned transparent electrode Indium Tin Oxide (ITO) glass was ultrasonically cleaned with deionized water (detergent), acetone, and isopropyl alcohol sequentially for 15mins. Spin-coating PEI-Zn electron transport layer on the cleaned ITO glass sheet, heating at 3500 rpm and then 200 ℃ for 20mins, spin-coating PM6:BTP-eC9:PC 71 BM active layer solution (total concentration of 18.7mg/mL, mass ratio of 1:1:0.2, solvent of chloroform) on the above substrate at 1500 rpm, and annealing at 100 ℃ for 10mins. The substrate temperature of the blade coating was 90℃and the blade height was 150 μm and the blade coating speed was 15mm/s when the PEDOT: PSS alcohol dispersion was blade coated. The conductivity of the prepared film is 6.2X10 2 S/cm, and the work function is 4.9eV.
The voltage of the organic solar cell device prepared by the method of the example represents the voltage, the current density represents the current density, the device open circuit voltage V OC =0.65V of a small area (0.04 cm 2), the current density J SC＝21.15mA/cm2, the fill factor ff=0.54, and the efficiency pce=7.42%. The PEDOT-PSS ethanol dispersion liquid obtained by the ultrafiltration method is applied to the anode of the organic solar cell, and has poor performance. The reason for this is mainly that here the dispersion concentration of anionic PSS in alcohol is low (below 5 mg/mL), so that direct addition of an alcohol solvent thereto while removing PEDOT: PSS aqueous solvent tends to cause large aggregation, and even the same ultrasonic cell disruption treatment solution as in the previous example 3 is difficult to obtain a uniform non-aggregated PEDOT: PSS alcohol dispersion, and therefore it is not suitable as an electrode of an organic solar cell. In addition, this process relies on ultrafiltration and evacuation equipment, which is disadvantageous for lightweight production.
In general, the method for preparing the alcohol-phase conductive polymer by solvent exchange provided by the invention has the advantages of simple process, easiness in processing, compatibility of the prepared alcohol-phase conductive polymer solution with various processing surfaces and processing processes, and good application prospect in devices such as organic solar cells, antistatic coatings, thermoelectric devices and the like.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (8)
1. A method for preparing an alcohol phase conductive polymer by solvent exchange, comprising the steps of:
(1) Putting polyethylene dioxythiophene and an aqueous solution of para-anion polystyrene sulfonic acid into a semipermeable membrane bag, soaking the semipermeable membrane bag into a first alcohol solvent, and allowing the aqueous solvent to seep out of the semipermeable membrane bag and the first alcohol solvent to permeate into the semipermeable membrane bag due to the polarity difference of the aqueous solvent and the first alcohol solvent, so that solvent exchange is realized;
(2) Adding a second solvent into the semipermeable membrane bag, adding a second doping agent of ethylene glycol, generating cavitation effect in the liquid by using strong ultrasound, completely dispersing solid particles in the liquid by using an ultrasonic cell grinder, adding other types of para-anionic high-fluorine sulfonate ion polymers which are not contained in the semipermeable membrane bag, and stirring and doping to obtain the alcohol phase conductive polymer.
2. The method for preparing an alcohol phase conductive polymer by solvent exchange according to claim 1, wherein the ratio of the amount of polyethylene dioxythiophene to the amount of the substance to anionic polystyrene sulfonic acid in the aqueous solution is 1 (2.5-30).
3. The method of preparing an alcohol phase conductive polymer according to claim 1, wherein the first alcohol solvent in step (1) and the second alcohol solvent in step (2) are each independently selected from the group consisting of C1-C10 aliphatic alcohols, alicyclic alcohols, and aromatic alcohols.
4. An alcohol phase conductive polymer prepared by the method of any one of claims 1-3.
5. Use of the alcohol phase conductive polymer according to claim 4 for the preparation of films.
6. A film obtained by the use according to claim 5.
7. The film for use according to claim 6, wherein the film has a conductivity of 10 -4-103S cm-1 and a work function of 4.1 to 5.4eV.
8. Use of a film according to claim 6 or 7, in particular in solar cell electrodes, solar cell hole transport layers, antistatic films, thermoelectric devices or light emitting diodes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310183746.XA CN116239803B (en) | 2023-02-28 | 2023-02-28 | Preparation of alcohol-phase conductive polymer by solvent exchange, method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310183746.XA CN116239803B (en) | 2023-02-28 | 2023-02-28 | Preparation of alcohol-phase conductive polymer by solvent exchange, method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116239803A CN116239803A (en) | 2023-06-09 |
| CN116239803B true CN116239803B (en) | 2025-04-04 |
Family
ID=86627496
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310183746.XA Active CN116239803B (en) | 2023-02-28 | 2023-02-28 | Preparation of alcohol-phase conductive polymer by solvent exchange, method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116239803B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111393678A (en) * | 2020-03-27 | 2020-07-10 | 徐宁 | Method for preparing organic solvent dispersion liquid of aqueous polymer |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6692662B2 (en) * | 2001-02-16 | 2004-02-17 | Elecon, Inc. | Compositions produced by solvent exchange methods and uses thereof |
| DE10111790A1 (en) * | 2001-03-12 | 2002-09-26 | Bayer Ag | New polythiophene dispersions |
| TWI318633B (en) * | 2002-01-25 | 2009-12-21 | Agfa Gevaert | Composition containing a polymer or copolymer of a 3,4-dialkoxythiophene and non-aqueous solvent |
| KR20170030333A (en) * | 2015-09-09 | 2017-03-17 | 한국생산기술연구원 | Method for purification and solvent exchanging of conductive polymer solution, and conductive polymer film using thereby |
| CN114316223B (en) * | 2021-12-31 | 2022-09-27 | 华中科技大学 | Alcohol dispersion liquid of conductive polyethylene dioxythiophene and preparation method and application thereof |
-
2023
- 2023-02-28 CN CN202310183746.XA patent/CN116239803B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111393678A (en) * | 2020-03-27 | 2020-07-10 | 徐宁 | Method for preparing organic solvent dispersion liquid of aqueous polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116239803A (en) | 2023-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101661994B (en) | Method needing no vacuum process to prepare organic polymer solar cell | |
| CN111192965B (en) | Flexible transparent electrode, preparation method thereof and flexible solar cell prepared from flexible transparent electrode | |
| JP2017505531A (en) | Ink for forming a P layer in an organic electronic device | |
| CN108091766B (en) | A kind of preparation method of perovskite battery with n-type doped electron transport layer and TiO2 layer | |
| Chao et al. | GaAs nanowire/poly (3, 4-ethylenedioxythiophene): poly (styrenesulfonate) hybrid solar cells with incorporating electron blocking poly (3-hexylthiophene) layer | |
| CN114388698B (en) | A method for preparing high-efficiency perovskite solar cells assisted by pre-protonated aminopyridine | |
| WO2023124367A1 (en) | Alcohol dispersion of conductive polyethylene dioxythiophene, preparation method therefor and application thereof | |
| CN103956430A (en) | Polymer solar battery with inverted structure and manufacturing method thereof | |
| CN105870342B (en) | The method of interface processing preparation high-performance perovskite thin film | |
| CN103403906A (en) | Photovoltaic cells | |
| CN114086238B (en) | A kind of γ-Ga2O3 or Cu doped γ-Ga2O3 nanocrystal and its preparation method and use | |
| Wen et al. | Environmentally friendly cathode interlayer modification on edible bio‐acids with enhanced electron extraction and improved power conversion efficiency | |
| CN108767122A (en) | The preparation and its application of the mesoporous titanium dioxide film material of modified by graphene quantum dot | |
| CN105470396B (en) | A kind of organic solar batteries based on polyfluorene cathode interface self assembly anode plasma resonance effects and preparation method thereof | |
| CN111192966B (en) | Perovskite solar cell and preparation method thereof | |
| CN115275020B (en) | A high-efficiency all-polymer organic solar cell structure and preparation method thereof | |
| CN116239803B (en) | Preparation of alcohol-phase conductive polymer by solvent exchange, method and application | |
| CN108682744A (en) | A kind of preparation method of the high organic photovoltaic devices of interfactial work ergosphere electric conductivity | |
| CN110611015A (en) | Preparation method and application of two-dimensional lead iodide sheet | |
| CN113013339B (en) | Method for preparing transparent flexible electrode based on ionic liquid and flexible solar cell | |
| KR101543258B1 (en) | Inverted polymer solar cells with randomly nanostructured surface electrode and manufacturing method thereof | |
| CN103094494B (en) | A kind of method of modifying of underlayer electrode and application thereof | |
| CN116887647A (en) | A high-efficiency intrinsically stretchable organic solar cell and its preparation method | |
| CN110212096A (en) | Organic solar batteries and preparation method thereof based on the molybdenum trioxide hole transmission layer with light trapping structure | |
| CN116162901A (en) | Vacuum vapor deposition of high quality perovskite thin films and photovoltaic applications thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |