High concentration graphene / black phosphorene dual medium aqueous dispersion and methods of use and preparation

Abstract

The application provides a high-concentration graphene / black phosphorene double-medium aqueous dispersion and a use and preparation method, and the preparation method specifically comprises the following steps: preparing a graphene aqueous dispersion, preparing a black phosphorene aqueous dispersion, and preparing a black phosphorene-doped graphene-based mixed solution; a two-dimensional carbon conductive coating is constructed through graphene self-adhesion, a graphene / black phosphorene layer with considerable conductivity, toughness and adhesion can be obtained, the graphene / black phosphorene layer can be applied to various non-conductive substrates on a printed circuit board, and the graphene / black phosphorene layer has the characteristics of high-temperature resistance, via hole efficiency and the like. The method has low cost and simple process, and can be suitable for large-scale industrial production.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of nanomaterials, and particularly relates to a high-concentration graphene / black phosphorene double-medium aqueous dispersion and a use and preparation method. BACKGROUND

[0002] Graphene is a two-dimensional nanomaterial with a honeycomb lattice structure formed by carbon atoms through sp2 hybridization orbits and only one layer of carbon atoms in thickness. The unique structure of graphene endows it with many excellent properties, such as a high theoretical specific surface area (2630 m / g), an ultra-high electron mobility (up to 200000 cm / vs), a high thermal conductivity (6000 W / mK), a high Young's modulus (10 TPa) and a high light transmittance (up to 97%). Due to the structural and performance advantages, graphene has great application prospects in the fields of energy storage and conversion devices, nano-electronic devices, multifunctional sensors, flexible wearable electronics, electromagnetic shielding, corrosion prevention and the like. Black phosphorus has a sheet structure similar to that of graphene, but the atoms in the same layer are not in the same plane, but in a honeycomb-like wrinkle structure. The atoms in the layer have strong covalent bonds, and the atoms between the layers are combined through van der Waals force. The unique wrinkle structure makes the atomic structure of black phosphorus exhibit a large compression and stretching in the plane. At the same time, black phosphorus exhibits good electrical properties, such as carrier mobility.

[0003] In view of the flexibility and conductive properties of graphene and black phosphorene, graphene paste is added to black phosphorene to prepare a conductive double-medium paste. Further, by adjusting the charge, impregnation and drying, a graphene / black phosphorene self-adhesion conductive film is prepared on a non-metallic substrate. Then, through an electroplating process, the non-conductive substrate is changed into a conductive substrate. However, the preparation process is complex. SUMMARY

[0004] The present application aims to provide a high-concentration graphene / black phosphorene double-medium aqueous dispersion and a use and preparation method, which has the advantages of simple process in actual use. At the same time, by constructing a conductive coating through graphene self-adhesion, a graphene layer with considerable conductivity, toughness and adhesion can be obtained, which can be applied to the surfaces of various non-conductive substrates of printed circuit boards, and has the characteristics of high temperature resistance, via efficiency and the like. The method has low cost and simple process, and can be suitable for large-scale industrial production and application in the preparation of graphene conductive coating.

[0005] To solve the above technical problems, the technical scheme adopted by the present application is as follows:

[0006] The preparation method of the high-concentration graphene / black phosphorene double-medium aqueous dispersion specifically comprises the following steps:

[0007] Step 1, preparing a graphene water dispersant, the dispersant including a first dispersant and a second dispersant; the first dispersant including sodium carbonate solution, ethanol and one or more of surfactants sodium dodecylbenzenesulfonate, polyvinylpyrrolidone, sodium lignosulfonate, polyvinyl alcohol, polydimethylsiloxane, gamma-(2,3-epoxypropoxy) propyl trimethoxysilane and gamma-aminopropyl triethoxysilane;

[0008] The mass ratio of sodium carbonate solution, ethanol and surfactant is 5:50-200:4-14.

[0009] The second dispersant includes sodium bicarbonate, one or more of surfactants ethyl phenyl polyethylene glycol, polysorbate, nonylphenol polyoxyethylene ether, polyethylene glycol and nonylphenol polyoxyethylene phosphate; the mass ratio of sodium bicarbonate and surfactant is 1:10-15.

[0010] Step 2, preparing a black phosphorene dispersion liquid: adding black phosphorene powder into N,N-dimethylacryl urea for ice water bath ultrasonic treatment, taking the precipitated and dried black phosphorene nanosheet, adding the black phosphorene nanosheet into ethanol solution, and ultrasonic dispersing into aqueous solution through hydroxylation treatment to obtain a black phosphorene water dispersion liquid; the mass ratio of ethanol and water is 13:7.

[0011] Step 3, preparing a graphene microsheet water dispersion liquid: taking graphene microsheets, dividing them into two parts, respectively adding the first dispersant and the second dispersant in step 1, and then ultrasonic dispersing the two parts to obtain a graphene microsheet water dispersion liquid.

[0012] Step 4, preparing a black phosphorene doped graphene-based mixed solution: slowly adding the black phosphorene dispersion liquid into the first part of graphene water dispersion liquid under stirring, and after the addition is completed, performing twice refinement to obtain a black phosphorene / graphene dual medium water dispersion liquid.

[0013] The first refinement and the second refinement in steps 1-5 independently include sequentially performing preliminary refinement and secondary refinement; after the preliminary refinement, the black phosphorene doped graphene-based mixed solution in the solution is sampled with a graduated cylinder, and then left to stand for 24 hours, and the transparent layered liquid is layered <5 ml; after the secondary refinement, the solution is sampled with a graduated cylinder, and then left to stand for 24 hours, and the transparent layered liquid is layered <5 ml.

[0014] Further optimization, the graphene / black phosphorene dual medium water dispersion liquid is refined first; and the second part of graphene water dispersion liquid is added into the solution after the first refinement to perform concentration treatment, to obtain the high-concentration graphene / black phosphorene dual medium solution.

[0015] The concentration treatment comprises adding graphene to the first refined solution for second refinement, and adjusting the pH value of the second refined solution to 10-11, and the method further comprises performing the concentration treatment on the first refined solution for multiple cycles to obtain a high-concentration graphene solution with a concentration greater than 12 mg / mL and a particle size less than 1 mu m.

[0016] The first refinement and the second refinement each independently comprise sequentially performing preliminary refinement and secondary refinement, the particle size of graphene in the preliminary refined solution is less than 5 mu m, and the particle size of graphene in the secondary refined solution is less than 1 mu m.

[0017] It is further limited that the preliminary refinement device is selected from one or more of an ultrasonic cell disrupter, a ball mill and a high-speed shearing machine used in series, and the secondary refinement device is selected from one or more of a high-pressure homogenizer and a micro-jet homogenizer used in series.

[0018] When the preliminary refinement device is an ultrasonic cell disrupter, the ultrasonic power is 800W-1200W, and the processing time is 15min-25min.

[0019] When the preliminary refinement device is a ball mill, the rotation speed of the sand mill is 3000rpm-6000rpm, and the processing time is 60min-90min.

[0020] When the preliminary refinement device is a high-speed shearing machine, the shearing speed of the shearing machine is 10000rpm-30000rpm, and the processing time is 20min-30min.

[0021] When the secondary refinement device is a high-pressure homogenizer, the processing pressure is 1000bar-1500bar, and the processing flow rate is 0.3s / mL-0.5s / mL.

[0022] The adjustment range of the pH value of the first refined solution is 10.0-11.0, and one of the following is added to the first refined solution: ammonia water, sodium carbonate, sodium bicarbonate, sodium hydroxide and potassium hydroxide.

[0023] The application also discloses a high-concentration graphene / black phosphorene dual-medium aqueous dispersion prepared by the preparation method.

[0024] Meanwhile, the application also discloses an application of the high-concentration graphene / black phosphorene dual-medium aqueous dispersion.

[0025] Compared with the prior art, the application has the following beneficial effects:

[0026] The application provides a high-concentration graphene / black phosphorene double-mediator aqueous dispersion preparation and use method, and specifically comprises the following steps: preparing a graphene aqueous dispersant, preparing a black phosphorene aqueous dispersion, preparing a graphene aqueous dispersion, and preparing a black phosphorene-doped graphene-based mixed solution; a conductive coating is constructed through graphene self-adhesion, a graphene / black phosphorene double-mediator layer with considerable conductivity, toughness and adhesion can be obtained, and the graphene / black phosphorene double-mediator layer can be applied to the surfaces of various non-conductive substrates of printed circuit boards, such as epoxy glass fiber laminates, polyimide resin glass fiber laminates, polytetrafluoroethylene glass fiber laminates and phenolic resin paper-based laminates, and has the characteristics of high-temperature resistance and via hole efficiency. The method has low cost and simple process, and can be applied to large-scale industrial production and the application in the preparation of high-conductive coatings. BRIEF DESCRIPTION OF DRAWINGS

[0027] In order to more clearly illustrate the technical solutions of the embodiments of the application, the drawings needed to be used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the application, and therefore should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can also be obtained without creative labor on the basis of these drawings.

[0028] Figure 1 A state diagram of the graphene / black phosphorene double-mediator composite solution prepared in the application cases 1-5.

[0029] Figure 2 A specific experimental result diagram of the graphene / black phosphorene double-mediator composite solution prepared in the application cases 1-5 and the solution diluted by 1000 times and then left for one week.

[0030] Figure 3 A DTV test experimental board diagram of the application.

[0031] Figure 4 A state schematic diagram of the application on an epoxy glass fiber laminate and after electroplating for 10 min and 60 min.

[0032] Figure 5 A copper layer coverage diagram of the application in the holes of an epoxy glass fiber laminate after electroplating for 10 min.

[0033] Figure 6 A copper layer coverage diagram of the application in the holes of an epoxy glass fiber laminate after electroplating for 60 min. DETAILED DESCRIPTION

[0034] The following disclosure provides a number of different implementations or examples for implementing different structures of embodiments of the present application. In order to simplify the disclosure of embodiments of the present application, the components and arrangements of specific examples are described below. Of course, they are merely examples and the purpose is not to limit the embodiments of the present application. In addition, the embodiments of the present application can refer to reference numerals and / or reference letters in different examples, and such repetition is for the purpose of simplification and clarity, which does not indicate the relationship between the various implementations and / or arrangements discussed.

[0035] The embodiments of the present application are described in detail below with reference to the accompanying drawings.

[0036] Embodiment one

[0037] The present embodiment discloses a preparation method of high-concentration graphene / black phosphorus double-medium aqueous dispersion, which specifically comprises the following steps:

[0038] Step 1, preparing a graphene aqueous dispersant, which comprises a first dispersant and a second dispersant;

[0039] The first dispersant comprises one or more of sodium carbonate solution, ethanol and surfactant sodium cellulose derivative sodium dodecyl benzene sulfonate, polyvinylpyrrolidone, sodium lignosulfonate, polyvinyl alcohol, polydimethylsiloxane, gamma-(2,3-epoxypropoxy) propyl trimethoxysilane and gamma-aminopropyl triethoxysilane; wherein the mass ratio of sodium carbonate solution, ethanol and surfactant is 5:50-200:4-14;

[0040] In the present embodiment, it is preferred that sodium carbonate solution, ethanol and surfactant sodium cellulose derivative sodium dodecyl benzene sulfonate and polyvinylpyrrolidone are mixed for use;

[0041] The mass ratio of sodium carbonate solution, ethanol and surfactant is 5:50-200:5-14; preferably 5:75:14;

[0042] The following ratios can also be selected, such as: 5:60:10, 5:120:12, 5:180:14, 5:180:12, 5:200:14, 5:90:8, 5:100:5;

[0043] That is, in the quality ratio of sodium carbonate solution, ethanol and surfactant, the sodium carbonate solution is 5, and the ethanol and surfactant can be any one value in 50-200, and the surfactant can be 4-15.

[0044] Of course, in actual use, one or more of the following surfactants can be used alone: sodium dodecyl benzene sulfonate, polyvinyl pyrrolidone, sodium lignosulfonate, polyvinyl alcohol, polydimethylsiloxane, gamma-(2,3-epoxypropoxy) propyl trimethoxysilane and gamma-aminopropyl triethoxysilane;

[0045] In some preferred embodiments, the surfactant can also be used in any two-by-two combination, three-by-three combination or four-by-four combination.

[0046] The second dispersant includes one or more of sodium bicarbonate, surfactant ethyl phenyl polyethylene glycol, polysorbate, nonylphenol polyoxyethylene ether, polyethylene glycol, nonylphenol polyoxyethylene phosphate, and the mass ratio of the sodium bicarbonate and the surfactant is 1:10-15.

[0047] Specifically, the mass ratio can be 1:10, 1:11, 1:12, 1:13, 1:14 or 1:15.

[0048] Step 2, preparation of black phosphorene dispersion liquid: after the ground black phosphorene powder is added to N,N-dimethylacryl urea and subjected to ice water bath ultrasonic treatment, the precipitated and dried black phosphorene nanosheet is added to an ethanol solution, and the black phosphorene nanosheet is ultrasonically dispersed in an aqueous solution through hydroxylation treatment to obtain a black phosphorene aqueous dispersion liquid, and the mass ratio of the ethanol and water is 13:7.

[0049] Step 3, preparation of graphene microsheet aqueous dispersion liquid: the graphene microsheet is weighed and divided into two parts, which are respectively added to the first dispersant and the second dispersant in step 1, and then ultrasonically dispersed to obtain the graphene microsheet aqueous dispersion liquid.

[0050] Step 4, preparation of black phosphorene doped graphene-based mixed solution: the black phosphorene dispersion liquid is slowly added to the first graphene aqueous dispersion liquid under stirring, and after the addition is completed, the black phosphorene / graphene dual medium aqueous dispersion liquid is obtained after two refining processes.

[0051] In steps 1-5, the first refining and the second refining are included, the first refining and the second refining independently include sequentially performing preliminary refining and secondary refining, after the preliminary refining, the black phosphorene doped graphene-based mixed solution in the solution is sampled with a graduated cylinder, and then the solution is left to stand for 24 hours, the transparent layered liquid is layered <5 ml, and after the secondary refining, the solution is sampled with a graduated cylinder, and then the solution is left to stand for 24 hours, the transparent layered liquid is layered <5 ml.

[0052] Further optimization, the graphene / black phosphorene dual medium aqueous dispersion liquid is subjected to first refining, and the second graphene aqueous dispersion liquid is added to the solution after the first refining to perform concentration increasing treatment, to obtain the high-concentration graphene / black phosphorene dual medium solution.

[0053] The concentration treatment includes adding graphene to the first refined solution for second refinement, and adjusting the pH value of the second refined solution to 10-11, and the method further includes performing the concentration treatment on the first refined solution for multiple cycles to obtain a high-concentration graphene solution with a concentration greater than 12 mg / mL and a particle size less than 1 μm.

[0054] The first refinement and the second refinement each independently include sequentially performing preliminary refinement and secondary refinement, the graphene particle size in the preliminary refined solution is less than 5 μm, and the graphene particle size in the secondary refined solution is less than 1 μm.

[0055] Further optimization, the preliminary refinement device is selected from one or more of an ultrasonic cell disrupter, a ball mill, and a high-speed shearing machine used in series, and the secondary refinement device is selected from one or more of a high-pressure homogenizer and a micro-jet homogenizer used in series.

[0056] When the preliminary refinement device is an ultrasonic cell disrupter, the ultrasonic power is 800 W-1200 W, and the processing time is 15 min-25 min.

[0057] Preferably, the ultrasonic power is 1000 W, and the processing time is 20 min.

[0058] When the preliminary refinement device is a sand mill, the sand mill rotation speed is 3000 rpm-6000 rpm, and the processing time is 60 min-90 min.

[0059] Preferably, the sand mill rotation speed is 4000 rpm, and the processing time is 70 min.

[0060] When the preliminary refinement device is a high-speed shearing machine, the shearing speed of the shearing machine is 10000 rpm-30000 rpm, and the processing time is 20 min-30 min.

[0061] Preferably, the shearing speed of the shearing machine is 20000 rpm, and the processing time is 25 min.

[0062] When the secondary refinement device is a high-pressure homogenizer, the processing pressure is 1000 bar-1500 bar, and the processing flow rate is 0.3 s / mL-0.5 s / mL.

[0063] Preferably, the processing pressure is 1200 bar, and the processing flow rate is 0.4 s / mL.

[0064] The adjustment range of the pH value of the first refined solution is 10.0-11.0, which includes adding one of ammonia, sodium carbonate, sodium bicarbonate, sodium hydroxide, and potassium hydroxide to the first refined solution.

[0065] The pH value of the first refined solution is preferably adjusted to 11, and ammonia is added to the first refined solution; of course, in actual use, any one of ammonia, sodium carbonate, sodium bicarbonate, sodium hydroxide and potassium hydroxide can be used.

[0066] Embodiment 2

[0067] The embodiment discloses a high-concentration graphene / black phosphorene dual-medium aqueous dispersion solution, which is mainly prepared by the method described in Embodiment 1.

[0068] Embodiment 3

[0069] The embodiment discloses application of the high-concentration graphene / black phosphorene dual-medium aqueous dispersion solution, and the application is mainly applied to preparation of a dual-medium conductive black shadow liquid.

[0070] The embodiment mainly discloses a black shadow conductive liquid prepared from the graphene / black phosphorene dual-conductive medium high-concentration aqueous dispersion solution, and application of the prepared black shadow conductive liquid on an epoxy resin glass fiber cloth substrate, in particular, application of the prepared black shadow conductive liquid in preparation of a graphene / black phosphorene self-adhesion conductive coating.

[0071] The application further discloses a FR-4 plate material made of an epoxy resin and a glass fiber cloth laminated together, and a surface conductive method of the FR-4 plate material comprises the following steps:

[0072] Pre-micro-etching, pure water washing, first charge adjustment, pure water washing, first alkylation, first stabilization, soaking water washing, first drying, second charge adjustment, pure water washing, second alkylation, second stabilization, soaking water washing, second drying, first micro-etching, second micro-etching, pure water washing, drying and copper plating.

[0073] The processing conditions and control parameters of each link of the method are shown in the following table.

[0074]

[0075]

[0076]

[0077]

[0078] In order to facilitate further understanding of the application by those skilled in the art, the application is further described below in combination with specific implementation cases.

[0079] Specifically, cases 1-5 are prepared in the manner described in Example 1, and the preparation methods in cases 1-5 are the same, and the main difference is that the components and contents of the materials in steps 1-4 are different, as follows:

[0080] Case 1

[0081] In this case: the first dispersant includes sodium carbonate solution, ethanol and surfactant sodium cellulose derivative sodium dodecylbenzenesulfonate and polyvinylpyrrolidone; wherein the mass ratio of sodium carbonate solution, ethanol and surfactant is 2:50:4; the mass ratio of sodium dodecylbenzenesulfonate and polyvinylpyrrolidone is 1:1;

[0082] The second dispersant includes sodium bicarbonate, surfactant ethylphenyl polyethylene glycol, polysorbate and nonylphenol polyoxyethylene ether, and the mass ratio of sodium bicarbonate and surfactant is 1:11; the mass ratio of ethylphenyl polyethylene glycol, polysorbate and nonylphenol polyoxyethylene ether is 1:2:1.5.

[0083] First, the ground black phosphorene powder is added to N,N-dimethylacryl urea for ice water bath ultrasonic treatment, and then the precipitated and dried black phosphorene nanosheet is obtained. The black phosphorene nanosheet is added to an ethanol solution, and is ultrasonically dispersed into an aqueous solution by hydroxylation treatment to obtain a black phosphorene aqueous dispersion. The mass ratio of ethanol and water is 13:7; the mass ratio of black phosphorene nanosheet and ethanol solution is 1:49.

[0084] Then, according to the ratio of graphene and total dispersant: 3:250, 3 parts of graphene microsheet are weighed and divided into two parts, and added into 125 parts of the first dispersant and 125 parts of the second dispersant respectively, and then two parts are obtained to prepare a graphene microsheet aqueous dispersion.

[0085] Finally, the black phosphorene dispersion is slowly added to the first part of the graphene aqueous dispersion under stirring, and after the addition is completed, two times of refinement are carried out to obtain a black phosphorene / graphene dual medium aqueous dispersion.

[0086] Case 2

[0087] This case is basically similar to case 1, and the difference is that the first dispersant includes sodium carbonate solution, ethanol and surfactant polyvinylpyrrolidone; wherein the mass ratio of sodium carbonate solution, ethanol and surfactant is 5:75:5;

[0088] The second dispersant includes sodium bicarbonate and surfactant nonylphenol polyoxyethylene ether, and the mass ratio of sodium bicarbonate and surfactant is 1:12.

[0089] Case 3

[0090] The present case is basically similar to case 1, and the difference is that the first dispersant comprises sodium carbonate solution, ethanol and surfactant sodium cellulose derivative polydimethylsiloxane and γ-(2, 3-epoxy propoxy) propyl trimethoxysilane; wherein the mass ratio of sodium carbonate solution, ethanol and surfactant is 5:100:7; the mass ratio of polydimethylsiloxane and γ-(2, 3-epoxy propoxy) propyl trimethoxysilane is 1:1.2;

[0091] The second dispersant comprises sodium bicarbonate, surfactant polyethylene glycol and nonylphenol polyoxyethylene phosphate, and the mass ratio of sodium bicarbonate and surfactant is 1:13; the mass ratio of polyethylene glycol and nonylphenol polyoxyethylene phosphate is 1:1.

[0092] Case 4

[0093] The present case is basically similar to case 1, and the difference is that the first dispersant comprises sodium carbonate solution, ethanol and surfactant γ-aminopropyl triethoxysilane; wherein the mass ratio of sodium carbonate solution, ethanol and surfactant is 5:135:8;

[0094] The second dispersant comprises sodium bicarbonate, surfactant nonylphenol polyoxyethylene phosphate, and the mass ratio of sodium bicarbonate and surfactant is 1:14.

[0095] Case 5

[0096] The present case is basically similar to case 1, and the difference is that the first dispersant comprises sodium carbonate solution, ethanol and surfactant sodium cellulose derivative sodium dodecyl benzene sulfonate, polyvinyl pyrrolidone, sodium lignosulfonate, polyvinyl alcohol, polydimethylsiloxane, γ-(2, 3-epoxy propoxy) propyl trimethoxysilane and γ-aminopropyl triethoxysilane; wherein the mass ratio of sodium carbonate solution, ethanol and surfactant is 5:140:9;

[0097] Sodium cellulose derivative sodium dodecyl benzene sulfonate, polyvinyl pyrrolidone, sodium lignosulfonate, polyvinyl alcohol, polydimethylsiloxane, γ-(2, 3-epoxy propoxy) propyl trimethoxysilane and γ-aminopropyl triethoxysilane are added in the same amount;

[0098] The second dispersant comprises sodium bicarbonate, surfactant ethyl phenyl polyethylene glycol, polysorbate, nonylphenol polyoxyethylene ether, polyethylene glycol and nonylphenol polyoxyethylene phosphate, and the mass ratio of sodium bicarbonate and surfactant is 1:15;

[0099] Among them, the amount of surfactant ethyl phenyl polyethylene glycol, polysorbate, nonylphenol polyoxyethylene ether, polyethylene glycol and nonylphenol polyoxyethylene phosphate added is the same.

[0100] The high-concentration graphene / black phosphorus double-medium aqueous dispersion prepared in cases 1-5 was respectively subjected to stability and dispersibility tests, and the specific experimental results after one week of standing are shown in Figure 1 and Figure 2 ;

[0101] According to Figure 1 , the high-concentration graphene / black phosphorus double-medium aqueous dispersion prepared in case 1-4 was substantially not layered after standing, and the solution still presented a uniform dispersed state, indicating that the solution had good stability.

[0102] Figure 2 To further Figure 1 , the state of the high-concentration graphene / black phosphorus double-medium aqueous dispersion prepared in case 1-5 after being physically diluted by 1000 times was observed, and according to Figure 2 , the dispersion was stable and had a high concentration, meeting the requirements.

[0103] The present application monitors the quality of the graphene / black phosphorus double-medium composite liquid through the daisy chain test method, and the specific operation method is as follows:

[0104] The DTV test plate with a pore size of 0.4 mm is used to perform experiments according to normal parameters and processes;

[0105] The copper plating is performed in a Haas tank according to the following process: cleaning (30-60 seconds) -> water washing (20 seconds) -> micro-etching (20-60 seconds) -> water washing (20 seconds) -> acid immersion (30-60 seconds) -> copper plating (1A, 10 minutes;

[0106] After copper plating, the holes are dried with a hair dryer, and the copper plating in the holes at 25ASF and 10ASF is observed;

[0107] The quality of the composite liquid is determined according to the number of perforations.

[0108] The determination criteria are as follows:

[0109] If the number of perforations in the 25ASF region is >7 and the number of perforations in the 10ASF region is >6, the composite liquid is determined to be in an excellent state;

[0110] If the number of perforations in the 25ASF region is >6-6.5 and the number of perforations in the 10ASF region is >5-5.5, the composite liquid is determined to be in a good state;

[0111] If the number of perforations in the 25ASF region is >5-5.5 and the number of perforations in the 10ASF region is >4-4.5, the composite liquid is determined to be in a standard state;

[0112] If the number of perforations in the 25ASF region is >4-4.5 and the number of perforations in the 10ASF region is >3-3.5, the composite liquid is determined to be at the lower limit of operation;

[0113] 25 The number of holes in the 10 ASF area is less than 3, and the number of holes in the 25 ASF area is less than 4, and the composite liquid state is determined to be in an undesirable state.

[0114] The test results are shown in Table 1. Figure 3

[0115] Figure 3 The test results of the FR-4 material on the DTV test sheet are shown in Table 1.

[0116] After the graphene / black phosphorene composite liquid is treated twice on the holes with a 0.2mm, 0.3mm, 0.5mm, 0.6mm hole diameter on the FR-4 plate, the hole diameter is observed under a magnifying glass, and it is found that the carbon film has completely covered the inner wall of all the holes.

[0117] After constant current electroplating at a current density of 2A / dm2 for 10min, and then constant current electroplating at a current density of 2A / dm2 for 60min, as shown in Table 1. Figure 4 The minimum hole diameter can reach 0.2mm, the hole filling capacity is sufficient, the carbon film covering uniformity is good, there is no dew point, and there is no fault, which meets the use requirements in the field of thin and light non-conductive substrates.

[0118] The plated holes are cut along the center line of the holes and finely polished on a polishing machine, and then the hole diameter is observed under a metallographic microscope, and the copper layer covering condition in the hole of the FR-4 substrate after electroplating for 10min is shown in Table 1, and the copper layer covering condition in the hole of the FR-4 substrate after electroplating for 60min is shown in Table 1.

[0119] The present application first uses two kinds of two-dimensional carbon materials, graphene and black phosphorene, in the conductive of printed circuit board non-conductive substrates, and develops a graphene / black phosphorene double medium aqueous dispersion solution with high concentration, which solves the problems of poor water solubility of two-dimensional materials, difficult to block interlayer adhesion, and unsatisfactory concentration for practical application.

[0120] The 0.2mm hole diameter ratio through hole on the FR-4 substrate of the high-concentration graphene / black phosphorene double medium aqueous dispersion solution shows good hole filling capacity, and is expected to be applied in the field of light and thin circuit board materials.

[0121] ​While the preferred embodiments of the application have been described, additional variations and modifications can be made to these embodiments by those skilled in the art once they have the benefit of the present disclosure. Therefore, the appended claims are intended to encompass all such variations and modifications as falling within the scope of the application.

[0122] The preferred embodiments of the application described hereinabove are therefore to be considered in all respects as illustrative only and not restrictive in character, since the scope of the application includes any modifications within the spirit and scope of the application as defined in the following claims.

Claims

1. A method for preparing a high-concentration graphene / black phosphorus dual-media aqueous dispersion, characterized in that, Specifically comprising the following steps: Step 1, preparing a graphene water dispersant, the dispersant comprising a first dispersant and a second dispersant; the first dispersant comprising a sodium carbonate solution, ethanol and a surfactant, the surfactant being one or more of sodium dodecyl benzene sulfonate, polyvinylpyrrolidone, sodium lignosulfonate, polyvinyl alcohol, polydimethylsiloxane, gamma-(2,3-epoxypropoxy) propyl trimethoxysilane and gamma-aminopropyl triethoxysilane; Wherein, the mass ratio of the sodium carbonate solution, ethanol and surfactant is 5:50-200:4-14; The second dispersant comprising sodium bicarbonate and a surfactant, the surfactant being one or more of ethyl phenyl polyethylene glycol, polysorbate, nonylphenol polyoxyethylene ether, polyethylene glycol and nonylphenol polyoxyethylene phosphate, the mass ratio of the sodium bicarbonate and the surfactant being 1:10-15; Step 2, preparing a black phosphorene dispersion liquid: after the ground black phosphorene powder is added to N,N-dimethylacryl urea and subjected to ice water bath ultrasonic treatment, the precipitated and dried black phosphorene nanosheet is added to an ethanol solution, and the black phosphorene nanosheet is ultrasonically dispersed into an aqueous solution through hydroxylation treatment to obtain a black phosphorene dispersion liquid, the mass ratio of the ethanol and water being 13:7; Step 3, preparing a graphene microsheet water dispersion liquid: the graphene microsheet is weighed and divided into two parts, which are respectively added into the first dispersant and the second dispersant of step 1, and then the two parts of the first dispersant and the second dispersant added with the graphene microsheet are respectively ultrasonically dispersed and mixed to obtain a first graphene microsheet water dispersion liquid and a second graphene microsheet water dispersion liquid; Step 4, preparing a black phosphorene doped graphene-based mixed liquid: the black phosphorene dispersion liquid is slowly added dropwise into the first graphene microsheet water dispersion liquid under stirring, and after the dropwise addition is completed, two refinements are performed to obtain a black phosphorene / graphene dual medium water dispersion liquid; The two refinements in step 4 refer to first refinement and second refinement performed in sequence, and the first refinement and the second refinement independently comprise sequentially performing primary refinement and secondary refinement, after the primary refinement of the black phosphorene / graphene dual medium water dispersion liquid, the solution is sampled with a graduated cylinder and then left to stand for 24 hours, the transparent layered liquid is layered <5 ml, and after the secondary refinement of the black phosphorene / graphene dual medium water dispersion liquid, the solution is sampled with a graduated cylinder and then left to stand for 24 hours, the transparent layered liquid is layered <5 ml; The first refined black phosphorene / graphene dual medium water dispersion liquid is added with the second graphene microsheet water dispersion liquid for concentration increasing treatment to obtain a high-concentration black phosphorene / graphene dual medium water dispersion liquid; Wherein, the concentration increasing treatment comprises adding graphene to the first refined black phosphorene / graphene dual medium water dispersion liquid for second refinement, and adjusting the pH value of the second refined black phosphorene / graphene dual medium water dispersion liquid to 10-11, and the method further comprises performing the concentration increasing treatment on the first refined black phosphorene / graphene dual medium water dispersion liquid for multiple cycles to obtain a high-concentration black phosphorene / graphene dual medium water dispersion liquid with a concentration greater than 12 mg / mL and a particle size less than 1 μm; The graphene particle size in the primary refined black phosphorene / graphene dual-medium aqueous dispersion is less than 5 μm, and the graphene particle size in the secondary refined black phosphorene / graphene dual-medium aqueous dispersion is less than 1 μm.

2. The method for preparing the high-concentration graphene / black phosphorus dual-media aqueous dispersion according to claim 1, characterized in that: The primary refining equipment is selected from one or more of ultrasonic cell disruptor, ball mill and high-speed shearing machine used in series, and the secondary refining equipment is selected from one or more of high-pressure homogenizer and micro-jet homogenizer used in series.

3. The preparation method of the high-concentration graphene / black phosphorene dual-medium aqueous dispersion according to claim 2, characterized in that: when the primary refining equipment is an ultrasonic cell disruptor, the ultrasonic power is 800 W to 1200 W, and the processing time is 15 min to 25 min; when the primary refining equipment is a ball mill, the rotation speed of the ball mill is 3000 rpm to 6000 rpm, and the processing time is 60 min to 90 min; when the primary refining equipment is a high-speed shearing machine, the shearing rotation speed of the shearing machine is 10000 rpm to 30000 rpm, and the processing time is 20 min to 30 min; when the secondary refining equipment is a high-pressure homogenizer, the processing pressure is 1000 bar to 1500 bar, and the processing flow rate is 0.3 s / mL to 0.5 s / mL.

4. Use of high-concentration graphene / black phosphorene double-mediator aqueous dispersion, characterized in that: The high-concentration graphene / black phosphorene dual-medium aqueous dispersion prepared by the preparation method of the high-concentration graphene / black phosphorene dual-medium aqueous dispersion according to any one of claims 1 to 3 is used for preparing a dual-medium conductive black shadow liquid.

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