CN111106252A

CN111106252A - Application of cathode interface material, three-dimensional composite material and preparation method thereof, optoelectronic device and preparation method thereof

Info

Publication number: CN111106252A
Application number: CN201911266582.7A
Authority: CN
Inventors: 吕梦岚; 陈希文; 潘飞; 李永舫
Original assignee: Guizhou Institute of Technology
Current assignee: Guizhou Institute of Technology
Priority date: 2019-12-11
Filing date: 2019-12-11
Publication date: 2020-05-05
Anticipated expiration: 2039-12-11
Also published as: CN111106252B

Abstract

The invention relates to the technical field of optoelectronic devices, in particular to the application of cathode interface materials, three-dimensional composite materials and preparation methods thereof, optoelectronic devices and preparation methods thereof. The cathode interface material can effectively disperse carbon nanomaterials and reduce the aggregation of carbon nanomaterials. At the same time, the three-dimensional composites formed by carbon nanomaterials dispersed in the cathode interface material solution can significantly improve the photoelectric conversion efficiency of optoelectronic devices.

Description

Application of cathode interface material, three-dimensional composite material and preparation method thereof, and photoelectric device and preparation method thereof

Technical Field

The invention relates to the technical field of photoelectric devices, in particular to application of a cathode interface material, a three-dimensional composite material and a preparation method thereof, and a photoelectric device and a preparation method thereof.

Background

Organic solar cells have become one of the most promising renewable energy technologies. The photovoltaic material based on the organic semiconductor has flexible mechanical properties, a general chemical structure, light weight and low cost. Due to the characteristics, the glass has the potential of becoming energy sources such as transparent power generation glass, zero-emission buildings, new energy vehicles, energy recycling public places and the like. In recent years, with the development of high-efficiency organic semiconductor technology and the advancement of device manufacturing technology, research on organic solar cells has received much attention.

There are two main types of organic semiconductors currently used in photovoltaic devices, small organic molecule acceptor materials and conjugated polymer donor materials. Non-fullerene small molecule acceptors are often chosen as electron acceptor materials, since their processing is well known, their structural plasticity is strong and they are more closely matched to the energy levels of the polymer donor material, making efficient charge transfer easier to achieve. Another key factor in the preparation of high performance organic photovoltaic devices is the use of interface materials. Due to the unique properties and advantages of the alcohol/water soluble interface material, the method comprises the steps of lower work function modification, charge recombination inhibition, effective charge extraction improvement and the like. Are successfully used in electron transport layers for polymer light emitting diodes and organic photovoltaics.

Graphene is a carbon nanomaterial, has high specific surface area, excellent thermal/electrical properties, high carrier mobility and transparency, mechanical flexibility, and compatibility with solution processing, and has been used in the fields of energy, composite materials, electronics, and the like. Meanwhile, based on the graphene semi-metal band structure capable of continuously adjusting the Fermi level, the work function of the graphene semi-metal band structure can be adjusted and controlled in a large range. They have high performance in optoelectronic devices and have been improved for use in electrode and interface materials. Therefore, the development of an effective surfactant and a dispersion method are of great significance to the mass production and practical application of the carbon nanomaterial.

In view of this, the invention is particularly proposed.

Disclosure of Invention

The invention aims to provide application of a cathode interface material, a three-dimensional composite material and a preparation method thereof, and a photoelectric device and a preparation method thereof.

In a first aspect, the present invention provides a novel application of a cathode interface material, which can effectively disperse a carbon nanomaterial, particularly graphene, and prevent aggregation thereof.

In a second aspect, the present invention further provides a three-dimensional composite material, which includes a cathode interface material and a carbon nanomaterial, wherein the carbon nanomaterial is uniformly dispersed in a solution of the cathode interface material, and the three-dimensional composite material can effectively improve photoelectric conversion efficiency of a photoelectric device.

In a third aspect, the present invention also provides a method for preparing a three-dimensional composite material, comprising: the carbon nanomaterial is dispersed in a solution of the cathode interface material.

In a fourth aspect, the present invention also provides a method for preparing an optoelectronic device, comprising spin coating the above three-dimensional composite material on a cathode or an active layer.

In a fifth aspect, the present invention also provides a photoelectric device, which is prepared by the above method for preparing a photoelectric device.

The invention has the following beneficial effects: the invention can well disperse the carbon nano material by utilizing the cathode material and can effectively prevent the carbon nano material from gathering. Meanwhile, the three-dimensional composite material prepared by dispersing the carbon nano material in the solution of the cathode interface material can obviously improve the photoelectric conversion efficiency of the photoelectric device.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.

FIG. 1 is a graph showing the results of detection in Experimental example 1;

FIG. 2 is a graph showing the detection result of XPS of Experimental example 2;

FIG. 3 is a graph showing the results of detection of AFM in Experimental example 2;

FIG. 4 is a graph showing the results of Tyndall effect measurement in Experimental example 2;

FIG. 5 is a Raman spectrum of Experimental example 2;

FIG. 6 is a XRD detection result chart of Experimental example 2;

FIG. 7 is a schematic view of a theoretical model for calculation of the three-dimensional composite material of example 1;

FIG. 8 is a schematic view of a theoretical model for calculation of the three-dimensional composite material of example 2;

FIG. 9 is a J-V curve of the conductivity of various materials of Experimental example 4;

FIG. 10 shows AM1.5G, 100mW/cm for a solar cell of Experimental example 6 using different cathode interface modification layers²J-V curve under illumination;

fig. 11 is a graph of external quantum efficiency of solar cells using different cathode interface modification layers of experimental example 6.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The features and properties of the present invention are described in further detail below with reference to examples.

First, the present implementation provides a new application of a cathode interface material, which can be used to disperse carbon nanomaterials and effectively prevent the carbon nanomaterials from aggregating.

Specifically, the cathode interface material is selected from any one of the cathode interface materials represented by the following chemical formula:

wherein R is₁And R₂All represent side chain segments having a conjugated system and containing nitrogen or oxygen;

preferably, R₁Any one selected from the following structural formulas:

R₂any one selected from the following structural formulas:

wherein R is₃Is a side chain containing nitrogen or oxygen;

preferably, R₃Any one selected from the following structural formulas:

wherein X is oxygen element or halogen element;

preferably, X is any one of oxygen, bromine and iodine;

preferably, the cathode interface material is selected from any one of the following formulas:

wherein R is

The cathode interface material can form good adsorption with the carbon nano material, so that the carbon nano material can be dispersed and stripped, the aggregation of the carbon nano material is prevented, and the application range of the cathode interface material is further expanded.

Wherein, the cathode interface material is

Wherein R is₁When the side chain segment containing nitrogen or oxygen and having a conjugated system is shown, the preparation steps of the cathode interface material comprise: the synthesis was carried out according to the following formula:

specifically, 1,3,5, 7-tetrakis (4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) phenyl) adamantane and a compound containing R₁Reacting a halogenated compound of a group to form said cathode interface material, further, preferably, reacting said 1,3,5, 7-tetrakis (4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) phenyl) adamantane with said compound containing R₁The molar ratio of halogenated compounds of groups is 5.8-6.2: 1; preferably, the synthesis of the 1,3,5, 7-tetrakis (4- (4,4,5, 5-tetramethyl-1, 3, 2-2-dioxaborane) phenyl) adamantane comprises reacting 1,3,5, 7-tetrakis (4-iodophenyl) adamantane, pinacol diborate diboride, potassium acetate and PdCl₂Mixing and reacting; preferably, the 1,3,5, 7-tetrakis (4-iodophenyl) adamantane, the pinacol diboron, the potassium acetate and the PdCl₂In a molar ratio of 1: (5.8-6.2): (14-16): (0.1-0.13). The effective synthesis of the cathode interface material can be ensured by adopting the synthesis conditions.

Further, the carbon nano material is a graphene material, preferably any one of a carbon nano tube and graphene; optionally, the carbon nanotubes comprise multi-walled carbon nanotubes and single-walled carbon nanotubes; optionally, the carbon nanotubes comprise heteroatom-doped carbon nanotubes; optionally, the graphene comprises multilayer graphene and single layer graphene; optionally, the graphene comprises heteroatom-doped graphene; most preferably, the carbon nanomaterial is single layer graphene.

In a further pair, when the carbon nano-material is dispersed in the cathode interface material solution, the maximum dispersion concentration of the carbon nano-material is 1.82-2.07mg/mL when the concentration of the cathode interface material is 1 mg/mL. Further illustrates that the cathode interface material can well disperse the carbon nano-material.

Secondly, the embodiment further provides a three-dimensional composite material, which includes the cathode interface material and the carbon nanomaterial, wherein the carbon nanomaterial is uniformly dispersed in a solution of the cathode interface material, and the three-dimensional composite material can effectively improve the photoelectric conversion efficiency of a photoelectric device.

Specifically, due to the unique spatial structure of the cathode interface material and the synergistic effect between the power supply performance of the pi-conjugated aromatic system and the amino side chain, the cathode interface material can well adsorb the carbon nano material, so that the formation of the three-dimensional composite material is ensured.

The cathode interface material and the carbon nanomaterial used in the three-dimensional composite material are the same as those used in the above-described application.

Further, when the carbon nanomaterial is dispersed in the cathode interface material solution and forms a three-dimensional composite material, the mass content of the carbon nanomaterial in the three-dimensional composite material is 1-20%. When the carbon nano material is in the content range, the three-dimensional composite material can be ensured to be capable of remarkably improving the photoelectric conversion efficiency of the photoelectric device.

Further, an embodiment of the present invention further provides a method for preparing a three-dimensional composite material, including: the carbon nanomaterial is dispersed in a solution of the cathode interface material. Specifically, the dispersing includes: and mixing the carbon nano material, the cathode interface material and a solvent to form a mixed solution, and then carrying out ultrasonic treatment to disperse the carbon nano material in the solution of the cathode interface material.

Among them, the solvent is an alcohol solvent, preferably a monohydric alcohol solvent, and more preferably an ethanol solvent. The ultrasonic treatment is a treatment performed at a low temperature of not higher than 15 ℃; alternatively, the ultrasonic treatment is a treatment carried out at a temperature of 0 to 15 ℃; alternatively, the ultrasonic treatment is a treatment carried out at a temperature of 0 to 5 ℃; optionally, the time of sonication is 30 minutes or more. The adoption of the conditions is more beneficial to the formation of the three-dimensional composite material, and the performance of the three-dimensional composite material is ensured.

Furthermore, the invention also provides a preparation method of the photoelectric device, which comprises the step of coating the three-dimensional composite material on a cathode or an active layer so as to improve the performance of the cathode or the active layer.

Further, the invention also provides a photoelectric device which is prepared by the preparation method of the photoelectric device. Optionally, the optoelectronic device comprises any one of a battery, a diode, a detector, a capacitor and a photovoltaic device; optionally, the cell comprises a solar cell and an electrochemical cell; optionally, the solar cell comprises any one of a tandem organic solar cell and a perovskite solar cell; optionally, the diode is an organic light emitting diode; optionally, the detector is a photodetector; optionally, the capacitor is a supercapacitor; optionally, the optoelectronic device is an organic photovoltaic device. Preferably, the photovoltaic device has an energy conversion efficiency of 15.6-15.8%.

Example 1

This example provides a three-dimensional composite material (numbered admaffn-G) comprising a cathode interface material and single-layer graphene dispersed in the cathode interface material, wherein the cathode interface material (numbered admaffn) has the following structural formula:

wherein R is

Wherein the loading amount of the single-layer graphene is 10%.

The synthesis process of the cathode interface material is as follows:

(1) synthesis of the Compound 1-1, 3,5, 7-tetrakis (4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) phenyl) adamantane

A round-bottomed flask was charged with 1,3,5, 7-tetrakis (4-iodophenyl) adamantane (944mg, 1mmol), pinacol ester diboron (1.53g, 6mmol), potassium acetate (1.5g, 15mmol), PdCl₂(dppf) (100mg, 0.12mmol), and 15mL of anhydrous DMSO, the mixture was deoxygenated by displacement of nitrogen for 15 minutes. The reaction was stirred at 80 ℃ for 12 hours, cooled to room temperature, and then 100mL of ice water was added. Extracting the mixture with chloroform, and extracting the organic phase with Na₂SO₄And (5) drying. The solvent was removed in vacuo and the residue was taken up in ethyl acetate/hexaneRecrystallization of the alkane gave compound 1 as a gray solid (645mg, 68%).¹HNMR(400MHz，CDCl₃)δ7.80(d，J＝8.0Hz，2H)，7.48(d，J＝8.0Hz，2H)，2.17(s，3H)，1.33(s，12H).¹³CNMR(100MHz，CDCl₃)δ152.51，135.01，124.48，83.71，46.93，39.49，24.85。

(2) Synthesis of the Compound 2- (9, 9-bis (3' - (N, N-dimethylamine) propyl) -2-bromofluorene

In a glove box under nitrogen atmosphere, 2-bromofluorene (3.0g, 12mmol), tetrabutylammonium bromide (80mg) and DMSO (50mL) were placed in a 250mL two-necked flask. The glove box was then removed and 12mL of aqueous sodium hydroxide and 20mL of 3-dimethylpropyl chloride in DMSO (5.0g, 32mmol) were injected. The reaction was stirred at 45 ℃ for 12 hours. After the reaction, 50mL of water was added to the mixture to remove inorganic salts in the system. The product was extracted three times with ethyl acetate, the organic layer was washed with water and brine respectively, dried over anhydrous sodium sulfate, and the solvent was removed under vacuum to give a crude product. Then, the column chromatography is carried out by gradient elution with methanol/dichloromethane (0-10%). Compound 2 is obtained.¹HNMR(400MHz，CDCl₃)δ7.68-7.62(m，1H)，7.54(d，J＝8.0Hz，1H)，7.48(s，1H)，7.44(dd，J＝8.0，1.2Hz，1H)，7.32(dt，J＝8.6，3.5Hz，3H)，2.05-1.94(m，20H)，0.81-0.71(m，4H).¹³CNMR(101MHz，CDCl₃)δ152.38，149.72，140.19，140.07，130.12，127.64，127.17，126.12，122.83，121.12，119.86，59.70，55.01，45.30，37.69，21.99。

(3) Synthesis of ADMAFN

Compound 1(125mg, 0.3mmol), compound 2(48mg, 0.05mmol), Pd (PPh) were added to a 15mL microwave reaction tube₃)₄(10mg) of the catalyst, and potassium carbonate (690mg, 5mmol) were deoxidized for 15 minutes, and the mixture was reacted at 110 ℃ for 5 hours in a microwave reactor. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted three times with toluene (10 mL. times.3). The organic phase was washed with water and brine three times, respectively, and dried over anhydrous sodium sulfate. After removal of the solvent under vacuum, the crude product is dissolved in dichloromethane and separated by TLC thin-layer chromatography using a developing solvent of twoMethyl chloride: methanol: triethylamine 100: 10: 3. 45mg of the final product ADMAFN (51%) were obtained.¹HNMR(400MHz，CDCl₃)δ7.84-7.52(m，8H)，7.40-7.27(m，3H)，2.35(s，3H)，2.12-1.84(m，20H)，0.92-0.73(m，4H).¹³CNMR(100MHz，CDCl₃)δ150.82，150.35，148.39，140.88，140.41，139.87，139.87，139.60，127.18，127.01，126.10，125.56，122.84，121.35，120.02，119.82，59.83，54.82，47.50，45.26，39.31，37.85，22.03.

The embodiment of the invention also provides a preparation method of the three-dimensional composite material, which comprises the following steps:

0.02 mg of single-layer graphene, 0.2 mg of cathode interface material and 1mL of ethanol are mixed, and then ultrasonic treatment is carried out, wherein the ultrasonic treatment temperature is 0 ℃, and the ultrasonic time is more than 30 minutes.

Example 2

A three-dimensional composite material (numbered POSSFN-G) was prepared by referring to the preparation method of example 1, except that the structural formula of the cathode interface material (numbered POSSFN) was as follows

R is

And the synthesis of the cathode interface material is disclosed in the patent number: the application of CN201610817239.7, other substances and operating conditions were not changed.

Example 3

A three-dimensional composite material was prepared by referring to the preparation method of example 1, except that single-layer graphene was replaced with double-layer graphene, and other substances and operation conditions were not changed.

Example 4

The three-dimensional composite material was prepared by referring to the preparation method of example 1, except that the cathode interface material was POSSFN, and other materials and operation conditions were not changed.

Example 5-example 7

The three-dimensional composite of example 1 was prepared except that the operating conditions during the preparation were varied. Specifically, the method comprises the following steps:

example 5: the loading amount of the single-layer graphene is 1%, the ultrasonic temperature is-5 ℃, and the ultrasonic time is more than 30 minutes.

Example 6, the loading of single-layer graphene was 10%, the sonication temperature was 0 ℃, and the sonication time was 30 minutes or more.

Example 7, the loading of single-layer graphene was 20%, the sonication temperature was 5 ℃, and the sonication time was 30 minutes or more.

Comparative example 1: the three-dimensional composite was prepared according to the preparation method of example 1, except that: the substance loaded on the single-layer graphene is a linear material poly (p- (N, N-dimethylamino) styrene) (numbered as PSN), and the three-dimensional composite material prepared from PSN is numbered as PSN-G.

Comparative example 2: single layer graphene provided for example 1.

Experimental example 1

The dispersion performance of the cathode interface materials of comparative example 1, example 1 and example 2 on graphene was examined

Respectively dispersing graphene in ethanol solutions of the cathode interface materials of comparative example 1, example 1 and example 2, then carrying out ultrasonic treatment, directly carrying out detection after ultrasonic treatment, and calculating the concentration of the graphene at the absorption spectrum of 660 nm.

Referring to fig. 1, it can be seen from fig. 1 that as the concentration of the cathode interface material or the linear material increases, the concentration of the graphene increases first and then decreases. After optimization, the maximum dispersion concentration of the graphene is 1.38mg/mL when the PSN concentration is 4 mg/mL; when the concentration of the ADMAFN is 1mg/mL, the maximum dispersion concentration of the graphene is 1.82 mg/mL; when the POSSFN is 1mg/mL, the maximum dispersion concentration of the graphene is 2.07 mg/mL. The relatively high concentration dispersibility of the cathode interface material to graphene in an alcohol phase system is very important in many applications where low boiling point green solvents are used.

Experimental example 2

X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), Atomic Force Microscopy (AFM) and the Tyndall effect are used for characterizing the dispersion characteristics of PSN, ADMAFN and POSSFN on graphene.

The detection results are shown in FIGS. 2 to 6. Fig. 2 is a graph showing XPS detection results of graphene; FIG. 3 is a graph showing the result of AFM detection; FIG. 4 is a graph showing the detection result of the Tyndall effect; FIG. 5 is a Raman spectrum; fig. 6 is a diagram of XRD detection results.

From FIG. 2, it can be seen that sp in the graphene lattice²The peak of the hybrid C-C double bond binding energy appears at 284.5eV, and occupies the dominant position. sp³The weaker binding energy peak of the hybridized C-C single bond appears at 285.3eV, which confirms that the defect content of the graphene sheet layer is lower.

As can be seen from fig. 3, after ADMAFN dispersion, the graphene has a lateral dimension of about 300nm and a thickness of about 1.24 nm. According to the thickness distribution of 50 graphene sheets, the average thickness of most graphene sheets is 1.657nm, and the graphene sheets are mainly single-layer graphene.

Fig. 5 shows (a) a raman spectrum of graphene without a dispersant, that is, a cathode interface material, (b) a raman spectrum of PSN dispersed graphene, (c) a raman spectrum of ADMAFN dispersed graphene, and (d) a raman spectrum of POSSFN dispersed graphene. As can be seen from fig. 5, the D peak due to edge/defect in the graphene lattice appears at 1344cm^-1(ii) is sp²The G peak caused by hybridized C ═ C double bond appears at 1583cm^-1Location. The 2D peak appears at 2689cm^-1The intensity ratio of the G peak, which correlates with the number of layers of graphene, confirms the formation of a small amount of layered graphene in the three-dimensional composite.

As can be seen from fig. 6, the single-layer graphene has a sharp diffraction peak at 26.4 °, whereas the PSN, ADMAFN and POSSFN-dispersed graphene (10 wt% graphene in 1mg/mL cathode interface material solution) does not have any diffraction peak in the range of 10 to 40 °, indicating that few-layer or single-layer graphene is combined.

Experimental example 3

In order to verify that the three-dimensional composite materials of examples 1 to 2 can be theoretically prepared and that the cathode interface material can disperse the carbon nanomaterial, the inventor calculates the adsorption energy of the corresponding cathode interface material on the single-layer graphene and the double-layer graphene and simultaneously performs the preparation by using molecular dynamics and standard periodic boundary conditions and periodic density functional theory. See table 1 and fig. 7-8 for analytical results.

Fig. 7 is a theoretical model of the three-dimensional composite material according to example 1, wherein a in fig. 7 is a schematic side view of the three-dimensional composite material, and b in fig. 7 is a schematic top view of the three-dimensional composite material. Fig. 8 is a theoretical model of the three-dimensional composite material according to example 2, wherein a in fig. 8 is a schematic side view of the three-dimensional composite material, and b in fig. 8 is a schematic top view of the three-dimensional composite material.

TABLE 1

According to the results, the adsorption energy of the cathode interface materials POSSFN (-6.37eV) and ADMAFN (-4.01eV) to the single-layer graphene is far larger than that of the linear material PSN (-0.64 eV). Compared with ADMAFN, POSSFN has a larger adsorption energy. The method is characterized in that the unique space structure of the three-dimensional material and the synergistic effect of the power supply performance of a pi-conjugated aromatic system and an amino side chain enable the adsorption energy of the POSSFN material on the surface of graphene to be larger than that of the ADMAFN material with a rigid main core.

Experimental example 4

The conductivity of pure PSN, ADMAFN, POSSFN, the three-dimensional composite materials of the embodiment 1, the embodiment 2 and the comparative example 1 is measured by adopting a space charge current limiting method (SCLC), and the structure of the device is ITO/graphene composite material/Al.

Referring to fig. 9, it can be seen from the results of the detection that the insulating materials PSN, ADMAFN and POSSFN become semiconductor materials after the graphene is added, and the conductivity is increased to 3.05 × 10^-5S/cm (comparative example 1), 6.09X 10^-5S/cm (example 1), 1.41X 10^-4S/cm (example 2).

Experimental example 5

The work functions of the three-dimensional composites of example 1, example 2 and comparative example 1 on various substrates were measured using a scanning kelvin microscope (scanning kelvin probe microscopy). The results are shown in tables 2 to 4.

TABLE 2 work function measured on different substrates with PSN-G of graphene at different ratios

TABLE 3 work function of ADMAFN-G with different ratios of graphene measured on different substrates

TABLE 4 work function of POSSFN-G with different proportions of graphene measured on different substrates

As can be seen from tables 2 to 4, the work functions of PSN-G on the ITO and evaporated silver electrodes are reduced to 4.06-4.17eV, the work function on the evaporated silver electrode is reduced to 3.55-3.80eV., the work functions of the three-dimensional composite material AMDAFN-G on the ITO electrode and the evaporated gold electrode are reduced by about-0.90 eV, and the work function on the evaporated silver electrode is reduced by about 0.92-1.01eV., and the work functions of the three-dimensional composite material POSSFN-G on the ITO electrode, the evaporated gold electrode and the evaporated silver electrode are reduced by about 0.40-0.64 eV.

Experimental example 6

A classical active layer system is selected, a donor material adopts PM6, an acceptor material is Y6, the three-dimensional composite materials of the embodiment 1, the embodiment 2 and the comparative example 1 are utilized to prepare photovoltaic devices with the structures of ITO/PEDOT: PSS-GO/PM6: Y6/composite material/Al (100nm), and then photoelectric conversion efficiency detection is carried out, and the detection results are shown in figures 10-11 and table 5.

TABLE 5 test results

From the above-mentioned detection results, it is found that the device energy conversion efficiency (PCE) obtained by directly using aluminum as a cathode interface material is 13.55% (Voc ═ 0.842V, Jsc ═ 22.54 mA/cm)²FF 71.38%), PCE of 14.79% (Voc 0.845V, Jsc 24.49 mA/cm) using PSN as cathode interface modification material²FF 71.47%), PCE 15.15% using ADMAFN as cathode interface modification material (Voc 0.851V, Jsc 24.43 mA/cm)²FF 72.87%), PCE of 15.03% (Voc 0.853V, Jsc 24.24 mA/cm) using POSSFN as cathode interface modification material²FF 72.66%). When a cathode interface modified composite material containing graphene is used as a cathode interface modified layer, the PCE of the PSN-G material is 15.38% (Voc ═ 0.846V, Jsc ═ 24.57 mA/cm)²FF 74.01%), PCE of ADMAFN-G material 15.81% (Voc 0.845V, Jsc 24.98mA/cm²FF 74.91%), PCE of POSSFN-G material 15.60% (Voc 0.849V, Jsc 24.85 mA/cm)²And FF is 73.93%), which shows that the three-dimensional composite material can improve the photoelectric conversion efficiency of the photovoltaic device.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. Application of a cathode interface material in dispersing carbon nanomaterials.

2. The application according to claim 1, wherein the cathode interface material is selected from any one of the cathode interface materials represented by the following chemical formula:

Wherein, R ₁ and R ₂ both represent fragments with a conjugated system and a side chain containing nitrogen or oxygen;

Preferably, R ₁ is selected from any one of the following structural formulas:

R ₂ is selected from any one of the following structural formulas:

Wherein, R ₃ is a side chain containing nitrogen or oxygen;

Preferably, _R is selected from any one of the following structural formulas:

Wherein, X is oxygen element or halogen element;

Preferably, X is any one of oxygen element, bromine element and iodine element;

Preferably, the cathode interface material is selected from any one of the following chemical formulas:

where R is

3. application according to claim 1, is characterized in that, described carbon nanomaterial is graphene material, is preferably any one in carbon nanotube and graphene;

Preferably, the carbon nanotubes include multi-walled carbon nanotubes and single-walled carbon nanotubes;

Preferably, the carbon nanotubes comprise heteroatom-doped carbon nanotubes;

Preferably, the graphene includes multi-layer graphene and single-layer graphene;

Preferably, the graphene comprises heteroatom-doped graphene;

Most preferably, the carbon nanomaterial is monolayer graphene.

4. The application according to claim 1, wherein the application is to disperse the carbon nanomaterial in a solution of the cathode interface material,

Preferably, the solution of the cathode interface material is an alcohol solution of the cathode interface material, more preferably, the solution of the cathode interface material is an ethanol solution of the cathode interface material;

Preferably, when the concentration of the cathode interface material is 1 mg/mL, the maximum dispersion concentration of the carbon nanomaterial is 1.82-2.07 mg/mL.

5. A three-dimensional composite material, characterized in that it comprises the cathode interface material according to any one of claims 2-4 and the carbon nanomaterial, and the carbon nanomaterial is uniformly dispersed in the cathode interface material. in solution.

6 . The three-dimensional composite material according to claim 5 , wherein the mass content of the carbon nanomaterial in the three-dimensional composite material is 1-20%. 7 .

7. The method for preparing a three-dimensional composite material according to claim 5 or 6, wherein the method comprises: dispersing the carbon nanomaterial in the solution of the cathode interface material.

8. The preparation method according to claim 7, wherein dispersing comprises: mixing the carbon nanomaterial, the cathode interface material and a solvent to form a mixed solution, and then performing low-temperature ultrasonic treatment, so that the carbon nanomaterial is dispersed in the solution of the cathode interface material;

Preferably, the solvent is an alcohol solvent, preferably a monohydric alcohol solvent, more preferably an ethanol solvent;

Preferably, the ultrasonic treatment is carried out at a temperature not higher than 15°C;

Preferably, the ultrasonic treatment is carried out at a temperature of 0-15°C;

More preferably, the ultrasonic treatment is carried out at a temperature of 0-5°C;

Preferably, the time of ultrasonic treatment is more than 30 minutes;

The preparation method further includes the preparation of the cathode interface material;

Preferably, when the cathode interface material is

Wherein, when R ₁ represents a side chain with a conjugated system and containing nitrogen or oxygen, the preparation steps of the cathode interface material include: synthesizing according to the following formula:

Preferably, the preparation of the cathode interface material includes: 1,3,5,7-tetrakis(4-(4,4,5,5-tetramethyl-1,3,2-2-dioxaborane)benzene) base) adamantane reacts with a halogenated compound containing an R ₁ group to form the cathode interface material;

Preferably, the 1,3,5,7-tetrakis(4-(4,4,5,5-tetramethyl-1,3,2-2-dioxaborane)phenyl)adamantane is combined with the The molar ratio of the halogenated compound containing the R ₁ group is 5.8-6.2:1;

Preferably, the synthesis of the 1,3,5,7-tetrakis(4-(4,4,5,5-tetramethyl-1,3,2-2-dioxaborane)phenyl)adamantane Including the mixed reaction of 1,3,5,7-tetrakis(4-iodophenyl)adamantane, pinacol biboronate, potassium acetate and _PdCl2 ;

Preferably, the molar ratio of the 1,3,5,7-tetrakis(4-iodophenyl)adamantane, the pinacol diboronate, the potassium acetate and the PdCl is ₁ :(5.8 -6.2): (14-16): (0.1-0.13).

9 . A method for preparing an optoelectronic device, comprising coating the three-dimensional composite material of claim 5 on the cathode or the active layer. 10 .

10. An optoelectronic device, characterized in that, it is prepared by the method for preparing an optoelectronic device according to claim 9,

Preferably, the optoelectronic device comprises any one of a battery, a diode, a detector, a capacitor and a photovoltaic device;

Preferably, the battery includes a solar cell and an electrochemical cell;

Preferably, the solar cell includes any one of a stacked organic solar cell and a perovskite solar cell;

Preferably, the diode is an organic light emitting diode;

Preferably, the detector is a light detector;

Preferably, the capacitor is a super capacitor;

Most preferably, the optoelectronic device is a photovoltaic device;

Preferably, the energy conversion efficiency of the photovoltaic device is 15.6-15.8%.