Graphene conductive paste and preparation method and application thereof

Abstract

The invention discloses graphene conductive paste and a preparation method and application thereof. Relates to the technical field of conductive paste. Raw materials of the graphene conductive paste comprise the following components: graphene; an aminopyrimidine; an epoxy resin; a metal oxide; and a solvent. Amino and nitrogen-containing heterocyclic rings are introduced into the graphene through aminopyrimidine, so that the surface of the graphene has more polar functional groups, the dispersity of the graphene in a polar solvent is enhanced, the agglomeration phenomenon between graphene sheet layers is reduced, and the more uniform and stable conductive paste is formed. Besides, the amino group and the nitrogen-containing heterocyclic ring can be chemically bonded with functional groups in the base material, so that the interface bonding force between the graphene and the base material is enhanced, and the adhesiveness of the conductive paste on the base material can be improved.

Description

Technical Field

[0001] The present invention relates to the technical field of conductive pastes, and in particular to a graphene conductive paste and a preparation method and application thereof. Background Art

[0002] Printed Circuit Board (PCB) is an indispensable basic component in electronic devices and the main carrier for connecting electronic components. PCB boards are usually composed of substrates, copper foil layers and other auxiliary materials, and have good mechanical support and electrical connectivity. It forms a conductive path on the surface of the substrate by chemical etching, mechanical drilling and other methods, thereby realizing the electrical connection between electronic components. With the continuous miniaturization and functional integration of electronic products, the design and manufacturing process of PCB boards are also constantly improving. New PCB technologies such as multilayer boards, flexible boards and high-density interconnect (HDI) boards are gradually becoming mainstream. PCB boards are not only widely used in traditional electronic fields such as computers, communication equipment, and household appliances, but also play an important role in high-end fields such as automotive electronics, medical equipment, and aerospace.

[0003] Graphene conductive paste is a conductive material based on graphene. It uses the unique two-dimensional crystal structure and excellent conductive properties of graphene to form an efficient conductive network. Graphene is a two-dimensional material composed of a single layer of carbon atoms. It has extremely high electrical and thermal conductivity, as well as excellent mechanical strength and chemical stability. Therefore, graphene conductive paste shows broad application prospects in the fields of electronic devices, batteries, sensors and coatings. Graphene conductive paste is usually composed of graphene powder, conductive additives, binders and solvents. It is applied to the surface of the substrate through processes such as spraying, printing or coating to form a conductive film or conductive circuit. Compared with traditional metal conductive paste, graphene conductive paste not only provides excellent conductive properties, but also has lighter weight and better flexibility. Therefore, it has great application potential in emerging fields such as flexible electronics and wearable devices.

[0004] The application of graphene conductive paste in PCB boards is to utilize the excellent conductive properties of graphene to improve the electrical and mechanical properties of PCB boards. Traditional PCB boards mainly rely on copper foil as conductive materials. Although copper has excellent conductivity, it has certain limitations in weight, flexibility and corrosion resistance. Graphene conductive paste can effectively make up for these shortcomings, making PCB boards lighter, more flexible and better anti-oxidation while maintaining good conductive properties. In addition, the thermal conductivity of graphene also helps to improve the heat dissipation capacity of PCB boards, especially in high-power density electronic devices, where good heat dissipation performance is crucial for stabilizing equipment operation and extending service life. Therefore, the application of graphene conductive paste in PCB boards can not only improve electrical performance, but also improve mechanical performance and thermal management performance, making it have important application value in modern electronic manufacturing.

[0005] However, although graphene conductive slurry shows broad application prospects, existing graphene conductive slurry still faces the problem of insufficient conductivity and stability in practical applications. First of all, the dispersion of graphene in the slurry has a huge impact on the conductivity. Due to the strong van der Waals force between graphene sheets, it is easy to form agglomerations in the slurry. This agglomeration phenomenon will cause the conductive network to be discontinuous, thereby significantly reducing the conductivity. In addition, the sheet structure of graphene is more sensitive to environmental factors and is easily affected by oxidation and moisture, which will not only reduce the conductive performance, but also may lead to insufficient long-term stability of the slurry. Under extreme conditions such as high temperature and high humidity, the performance degradation problem of graphene is particularly prominent, which poses a challenge to its application in harsh environments. Summary of the invention

[0006] The object of the present invention is to provide a graphene conductive paste with good conductivity and high stability.

[0007] A first aspect of the present invention is:

[0008] Provided is a graphene conductive paste.

[0009] A second aspect of the present invention is:

[0010] Provided is a method for preparing a graphene conductive slurry.

[0011] The third aspect of the present invention is:

[0012] Application of the graphene conductive slurry.

[0013] The invention also provides a PCB board.

[0014] Specifically, the technical solution adopted according to the first aspect of the present invention is:

[0015] A graphene conductive slurry, the raw materials of which include the following components:

[0016] Graphene;

[0017] aminopyrimidine;

[0018] Epoxy resin;

[0019] Metal oxides;

[0020] Solvent.

[0021] According to the embodiments of the present invention, one of the technical solutions has at least one of the following advantages or beneficial effects:

[0022] The present invention introduces amino groups and nitrogen-containing heterocycles into graphene through aminopyrimidine, so that the surface of graphene has more polar functional groups, thereby enhancing the dispersibility of graphene in polar solvents, reducing the agglomeration phenomenon between graphene sheets, and forming a more uniform and stable conductive paste. In addition, amino groups and nitrogen-containing heterocycles can be chemically bonded with functional groups in the substrate, thereby enhancing the interfacial bonding force between graphene and the substrate, which helps to improve the adhesion of the conductive paste on the substrate, reduce the risk of peeling or cracking of the conductive layer, thereby improving the durability and reliability of the conductive layer. Finally, the introduction of metal oxides into the graphene conductive paste of the present invention can improve the conductivity of the paste.

[0023] According to one embodiment of the present invention, the raw materials of the graphene conductive paste include the following components in parts by weight:

[0024] Graphene, 8-20 parts;

[0025] Aminopyrimidine, 0.5-2 parts;

[0026] Epoxy resin, 20-30 parts;

[0027] Copper oxide, 3-8 parts;

[0028] Solvent, 75-85 parts.

[0029] According to one embodiment of the present invention, the aminopyrimidine includes at least one of 4-aminopyrimidine and 2-aminopyrimidine.

[0030] According to one embodiment of the present invention, the raw materials of the graphene conductive paste further include: polyaldehyde.

[0031] According to one embodiment of the present invention, the polyaldehyde is a polyaldehyde having 3 or more carbon atoms.

[0032] According to one embodiment of the present invention, the polyaldehyde is a combination of at least two polyaldehydes having carbon atoms greater than or equal to 3.

[0033] According to one embodiment of the present invention, the polyaldehyde includes at least one of succindialdehyde, glutaraldehyde, adipaldehyde, heptanedialdehyde and suberaldehyde.

[0034] The present invention introduces a polyaldehyde into the graphene conductive paste, and allows the polyaldehyde to react with the graphene modified by aminopyrimidine, so that the aldehyde group reacts with the amino group in the modified graphene to form a cross-linked network. However, due to the long length of the polyaldehyde and the different lengths and molecular structures of different polyaldehydes, the cross-linking reaction will cause uneven local tension of the graphene, causing the sheet to bend and deform, and finally forming a "trap" structure. This result helps to capture particles, such as copper oxide in the graphene conductive paste of the present invention, thereby improving the binding force of the components in the paste and further avoiding the agglomeration of graphene.

[0035] According to one embodiment of the present invention, the metal oxide includes copper oxide, and the copper oxide includes copper oxide modified by a silane coupling agent. After the copper oxide is modified by a silane coupling agent, active chemical groups such as amino groups and hydroxyl groups are formed on the surface, which are connected to the epoxy resin in the graphene conductive paste of the present invention through chemical bonds, which not only solves the agglomeration phenomenon of a large amount of copper oxide accumulated in the "trap", but also improves the interaction of the interface and establishes a more complete conductive network.

[0036] According to one embodiment of the present invention, the method for preparing the silane coupling agent modified copper oxide comprises the following steps: mixing copper oxide, xylene and a silane coupling agent, and subjecting the mixture to a heating treatment to obtain the silane coupling agent modified copper oxide.

[0037] According to one embodiment of the present invention, the solvent comprises water.

[0038] According to one embodiment of the present invention, the epoxy resin includes epoxy resin E20.

[0039] Specifically, the technical solution adopted according to the second aspect of the present invention is:

[0040] A method for preparing the graphene conductive slurry comprises the following steps:

[0041] S1, under a protective atmosphere, mixing aminopyrimidine, graphene and a solvent to obtain a first modified graphene through reaction;

[0042] S2: mixing the first modified graphene, epoxy resin and metal oxide to obtain the graphene conductive slurry.

[0043] According to one embodiment of the present invention, step S2 further includes the following steps: mixing and reacting the first modified graphene with a polyaldehyde to obtain a second modified graphene, and then mixing the second modified graphene with an epoxy resin and a metal oxide.

[0044] Another aspect of the present invention further provides a PCB board, including the graphene conductive paste as described in the first embodiment. Since the application adopts all the technical solutions of the graphene conductive paste, it has at least all the beneficial effects brought by the technical solutions of the above embodiment.

[0045] Other features and advantages of the present invention will be set forth in the description which follows, and in part will be apparent from the description, or may be learned by practice of the present invention. DETAILED DESCRIPTION

[0046] In the description of the present invention, if there is a description of first, second, etc., it is only for the purpose of distinguishing technical features, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features or implicitly indicating the order of the indicated technical features.

[0047] The words "preferably", "more preferably", etc. in the present invention refer to embodiments of the present invention that may provide certain beneficial effects in certain circumstances. However, other embodiments may also be preferred under the same circumstances or other circumstances. In addition, the description of one or more preferred embodiments does not imply that other embodiments are not applicable, nor is it intended to exclude other embodiments from the scope of the present invention.

[0048] When a numerical range is disclosed herein, the above range is considered to be continuous and includes the minimum and maximum values ​​of the range, as well as every value between such minimum and maximum values. Further, when a range refers to an integer, every integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be combined. In other words, unless otherwise indicated, all ranges disclosed herein should be understood to include any and all subranges included therein.

[0049] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of the present invention.

[0050] Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0051] Example 1

[0052] A graphene conductive slurry, the raw materials of which include the following components:

[0053] Graphene, 8 parts;

[0054] Aminopyrimidine, 0.5 part;

[0055] Epoxy resin, 20 parts;

[0056] Copper oxide, 3 parts;

[0057] Polyvinylpyrrolidone, 2 parts;

[0058] Water, 75 parts;

[0059] Wherein, aminopyrimidine is 2-aminopyrimidine;

[0060] Wherein, the epoxy resin is epoxy resin E20;

[0061] The method for preparing the above-mentioned graphene conductive slurry comprises the following steps:

[0062] S1, under a protective atmosphere, mixing 2-aminopyrimidine and graphene in water, adjusting the pH to 8, and stirring at 2° C. for 24 hours, and obtaining a first modified graphene after centrifugal drying;

[0063] S2: mixing copper oxide and water to obtain a copper oxide solution, adding the first modified graphene, stirring, adding epoxy resin E20 and polyvinyl pyrrolidone to obtain a graphene conductive slurry.

[0064] Example 2

[0065] The difference between Example 2 and Example 1 is that the raw materials of the graphene conductive paste of Example 2 also include polyaldehyde.

[0066] A graphene conductive slurry, the raw materials of which include the following components:

[0067] Graphene, 8 parts;

[0068] Aminopyrimidine, 0.5 part;

[0069] Epoxy resin, 20 parts;

[0070] Copper oxide, 3 parts;

[0071] Polyaldehyde, 8 parts;

[0072] Polyvinylpyrrolidone, 2 parts;

[0073] Water, 75 parts;

[0074] Wherein, aminopyrimidine is 2-aminopyrimidine;

[0075] Wherein, the epoxy resin is epoxy resin E20;

[0076] Wherein, the polyaldehyde is glutaraldehyde and adipaldehyde in a weight ratio of 1:1;

[0077] The method for preparing the above-mentioned graphene conductive slurry comprises the following steps:

[0078] S1, under a protective atmosphere, mixing 2-aminopyrimidine and graphene in water, adjusting the pH to 8, and stirring at 2° C. for 24 hours, and obtaining a first modified graphene after centrifugal drying;

[0079] S2: preparing a polyaldehyde solution with a total molar concentration of 3% of the polyaldehyde, mixing the polyaldehyde solution with the first modified graphene at a molar ratio of 1:1, and obtaining a second modified graphene after centrifugation and drying;

[0080] S3: mixing copper oxide and water to obtain a copper oxide solution, adding the second modified graphene, stirring, adding epoxy resin E20 and polyvinyl pyrrolidone to obtain a graphene conductive slurry.

[0081] Example 3

[0082] The difference between Example 3 and Example 2 is that in the raw material of the graphene conductive paste of Example 3, the copper oxide is copper oxide modified by y-aminopropyltriethoxysilane.

[0083] A graphene conductive slurry, the raw materials of which include the following components:

[0084] Graphene, 8 parts;

[0085] Aminopyrimidine, 0.5 part;

[0086] Epoxy resin, 20 parts;

[0087] Copper oxide, 3 parts;

[0088] Silane coupling agent, 0.3 parts;

[0089] Polyaldehyde, 8 parts;

[0090] Polyvinylpyrrolidone, 2 parts;

[0091] Water, 75 parts;

[0092] Wherein, aminopyrimidine is 2-aminopyrimidine;

[0093] Wherein, the epoxy resin is epoxy resin E20;

[0094] Wherein, the silane coupling agent is y-aminopropyltriethoxysilane;

[0095] Wherein, the copper oxide is copper oxide modified by y-aminopropyltriethoxysilane;

[0096] Wherein, the polyaldehyde is glutaraldehyde and adipaldehyde in a weight ratio of 1:1;

[0097] The method for preparing the above-mentioned graphene conductive slurry comprises the following steps:

[0098] S1, under a protective atmosphere, mixing 2-aminopyrimidine and graphene in water, adjusting the pH to 8, and stirring at 2° C. for 24 hours, and obtaining a first modified graphene after centrifugal drying;

[0099] S2: preparing a polyaldehyde solution with a total molar concentration of 3% of the polyaldehyde, mixing the polyaldehyde solution with the first modified graphene at a molar ratio of 1:1, and obtaining a second modified graphene after centrifugation and drying;

[0100] S3: Add copper oxide to 50 mL of xylene, heat to 90°C, add y-aminopropyltriethoxysilane, heat to 115°C, stir for 6 hours, filter and dry to obtain modified copper oxide;

[0101] S4: Mix the modified copper oxide and water to obtain a copper oxide solution, add the second modified graphene, stir, add epoxy resin E20 and polyvinyl pyrrolidone to obtain a graphene conductive slurry.

[0102] Example 4

[0103] The difference between Example 4 and Example 3 is that the polyaldehyde in Example 3 is glutaraldehyde.

[0104] A graphene conductive slurry, the raw materials of which include the following components:

[0105] Graphene, 8 parts;

[0106] Aminopyrimidine, 0.5 part;

[0107] Epoxy resin, 20 parts;

[0108] Copper oxide, 3 parts;

[0109] Silane coupling agent, 0.3 parts;

[0110] Polyaldehyde, 8 parts;

[0111] Polyvinylpyrrolidone, 2 parts;

[0112] Water, 75 parts;

[0113] Wherein, aminopyrimidine is 2-aminopyrimidine;

[0114] Wherein, the epoxy resin is epoxy resin E20;

[0115] Wherein, the silane coupling agent is y-aminopropyltriethoxysilane;

[0116] Wherein, the copper oxide is copper oxide modified by y-aminopropyltriethoxysilane;

[0117] Wherein, the polyaldehyde is glutaraldehyde;

[0118] The method for preparing the above-mentioned graphene conductive slurry comprises the following steps:

[0119] S1, under a protective atmosphere, mixing 2-aminopyrimidine and graphene in water, adjusting the pH to 8, and stirring at 2° C. for 24 hours, and obtaining a first modified graphene after centrifugal drying;

[0120] S2 prepares a polyaldehyde solution with a molar concentration of 3%, mixes the polyaldehyde solution with the first modified graphene at a molar ratio of 1:1, and obtains a second modified graphene after centrifugation and drying;

[0121] S3: Add copper oxide to 50 mL of xylene, heat to 90°C, add y-aminopropyltriethoxysilane, heat to 115°C, stir for 6 hours, filter and dry to obtain modified copper oxide;

[0122] S4: Mix the modified copper oxide and water to obtain a copper oxide solution, add the second modified graphene, stir, add epoxy resin E20 and polyvinyl pyrrolidone to obtain a graphene conductive slurry.

[0123] Example 5

[0124] The difference between Example 5 and Example 3 is that the polyaldehyde in Example 3 is adipaldehyde.

[0125] A graphene conductive slurry, the raw materials of which include the following components:

[0126] Graphene, 8 parts;

[0127] Aminopyrimidine, 0.5 part;

[0128] Epoxy resin, 20 parts;

[0129] Copper oxide, 3 parts;

[0130] Silane coupling agent, 0.3 parts;

[0131] Polyaldehyde, 8 parts;

[0132] Polyvinylpyrrolidone, 2 parts;

[0133] Water, 75 parts;

[0134] Wherein, aminopyrimidine is 2-aminopyrimidine;

[0135] Wherein, the epoxy resin is epoxy resin E20;

[0136] Wherein, the silane coupling agent is y-aminopropyltriethoxysilane;

[0137] Wherein, the copper oxide is copper oxide modified by y-aminopropyltriethoxysilane;

[0138] Wherein, the polyaldehyde is adipaldehyde in parts by weight;

[0139] The method for preparing the above-mentioned graphene conductive slurry comprises the following steps:

[0140] S1, under a protective atmosphere, mixing 2-aminopyrimidine and graphene in water, adjusting the pH to 8, and stirring at 2° C. for 24 hours, and obtaining a first modified graphene after centrifugal drying;

[0141] S2 prepares a polyaldehyde solution with a molar concentration of 3%, mixes the polyaldehyde solution with the first modified graphene at a molar ratio of 1:1, and obtains a second modified graphene after centrifugation and drying;

[0142] S3: Add copper oxide to 50 mL of xylene, heat to 90°C, add y-aminopropyltriethoxysilane, heat to 115°C, stir for 6 hours, filter and dry to obtain modified copper oxide;

[0143] S4: Mix the modified copper oxide and water to obtain a copper oxide solution, add the second modified graphene, stir, add epoxy resin E20 and polyvinyl pyrrolidone to obtain a graphene conductive slurry.

[0144] Example 6

[0145] The difference between Example 6 and Example 3 is that the amount of raw materials used in the graphene conductive slurry is different.

[0146] A graphene conductive slurry, the raw materials of which include the following components:

[0147] Graphene, 20 parts;

[0148] Aminopyrimidine, 2 parts;

[0149] Epoxy resin, 30 parts;

[0150] Copper oxide, 8 parts;

[0151] Silane coupling agent, 0.3 parts;

[0152] Polyaldehyde, 8 parts;

[0153] Polyvinylpyrrolidone, 2 parts;

[0154] Water, 85 parts;

[0155] Wherein, aminopyrimidine is 2-aminopyrimidine;

[0156] Wherein, the epoxy resin is epoxy resin E20;

[0157] Wherein, the silane coupling agent is y-aminopropyltriethoxysilane;

[0158] Wherein, the copper oxide is copper oxide modified by y-aminopropyltriethoxysilane;

[0159] Wherein, the polyaldehyde is glutaraldehyde and adipaldehyde in a weight ratio of 1:1;

[0160] The method for preparing the above-mentioned graphene conductive slurry comprises the following steps:

[0161] S1, under a protective atmosphere, mixing 2-aminopyrimidine and graphene in water, adjusting the pH to 8, and stirring at 2° C. for 24 hours, and obtaining a first modified graphene after centrifugal drying;

[0162] S2: preparing a polyaldehyde solution with a total molar concentration of 3% of the polyaldehyde, mixing the polyaldehyde solution with the first modified graphene at a molar ratio of 1:1, and obtaining a second modified graphene after centrifugation and drying;

[0163] S3: Add copper oxide to 50 mL of xylene, heat to 90°C, add y-aminopropyltriethoxysilane, heat to 115°C, stir for 6 hours, filter and dry to obtain modified copper oxide;

[0164] S4: Mix the modified copper oxide and water to obtain a copper oxide solution, add the second modified graphene, stir, add epoxy resin E20 and polyvinyl pyrrolidone to obtain a graphene conductive slurry.

[0165] Example 7

[0166] The difference between Example 7 and Example 3 is that the amount of raw materials used in the graphene conductive paste is different.

[0167] A graphene conductive slurry, the raw materials of which include the following components:

[0168] Graphene, 10 parts;

[0169] Aminopyrimidine, 0.8 part;

[0170] Epoxy resin, 20 parts;

[0171] Copper oxide, 3 parts;

[0172] Silane coupling agent, 0.3 parts;

[0173] Polyaldehyde, 8 parts;

[0174] Polyvinylpyrrolidone, 2 parts;

[0175] Water, 75 parts;

[0176] Wherein, aminopyrimidine is 2-aminopyrimidine;

[0177] Wherein, the epoxy resin is epoxy resin E20;

[0178] Wherein, the silane coupling agent is y-aminopropyltriethoxysilane;

[0179] Wherein, the copper oxide is copper oxide modified by y-aminopropyltriethoxysilane;

[0180] Wherein, the polyaldehyde is glutaraldehyde and adipaldehyde in a weight ratio of 1:1;

[0181] The method for preparing the above-mentioned graphene conductive slurry comprises the following steps:

[0182] S1, under a protective atmosphere, mixing 2-aminopyrimidine and graphene in water, adjusting the pH to 8, and stirring at 2° C. for 24 hours, and obtaining a first modified graphene after centrifugal drying;

[0183] S2: preparing a polyaldehyde solution with a total molar concentration of 3% of the polyaldehyde, mixing the polyaldehyde solution with the first modified graphene at a molar ratio of 1:1, and obtaining a second modified graphene after centrifugation and drying;

[0184] S3: Add copper oxide to 50 mL of xylene, heat to 90°C, add y-aminopropyltriethoxysilane, heat to 115°C, stir for 6 hours, filter and dry to obtain modified copper oxide;

[0185] S4: Mix the modified copper oxide and water to obtain a copper oxide solution, add the second modified graphene, stir, add epoxy resin E20 and polyvinyl pyrrolidone to obtain a graphene conductive slurry.

[0186] Example 8

[0187] The difference between Example 8 and Example 3 is that the amount of raw materials used in the graphene conductive slurry is different.

[0188] A graphene conductive slurry, the raw materials of which include the following components:

[0189] Graphene, 10 parts;

[0190] Aminopyrimidine, 1.5 parts;

[0191] Epoxy resin, 20 parts;

[0192] Copper oxide, 3 parts;

[0193] Silane coupling agent, 0.3 parts;

[0194] Polyaldehyde, 8 parts;

[0195] Polyvinylpyrrolidone, 2 parts;

[0196] Water, 75 parts;

[0197] Wherein, aminopyrimidine is 2-aminopyrimidine;

[0198] Wherein, the epoxy resin is epoxy resin E20;

[0199] Wherein, the silane coupling agent is y-aminopropyltriethoxysilane;

[0200] Wherein, the copper oxide is copper oxide modified by y-aminopropyltriethoxysilane;

[0201] Wherein, the polyaldehyde is glutaraldehyde and adipaldehyde in a weight ratio of 1:1;

[0202] The method for preparing the above-mentioned graphene conductive slurry comprises the following steps:

[0203] S1, under a protective atmosphere, mixing 2-aminopyrimidine and graphene in water, adjusting the pH to 8, and stirring at 2° C. for 24 hours, and obtaining a first modified graphene after centrifugal drying;

[0204] S2: preparing a polyaldehyde solution with a total molar concentration of 3% of the polyaldehyde, mixing the polyaldehyde solution with the first modified graphene at a molar ratio of 1:1, and obtaining a second modified graphene after centrifugation and drying;

[0205] S3: Add copper oxide to 50 mL of xylene, heat to 90°C, add y-aminopropyltriethoxysilane, heat to 115°C, stir for 6 hours, filter and dry to obtain modified copper oxide;

[0206] S4: Mix the modified copper oxide and water to obtain a copper oxide solution, add the second modified graphene, stir, add epoxy resin E20 and polyvinyl pyrrolidone to obtain a graphene conductive slurry.

[0207] Example 9

[0208] The difference between Example 9 and Example 3 is that the amount of raw materials used in the graphene conductive paste is different.

[0209] A graphene conductive slurry, the raw materials of which include the following components:

[0210] Graphene, 12 parts;

[0211] Aminopyrimidine, 1.5 parts;

[0212] Epoxy resin, 22 parts;

[0213] Copper oxide, 3 parts;

[0214] Silane coupling agent, 0.3 parts;

[0215] Polyaldehyde, 8 parts;

[0216] Polyvinylpyrrolidone, 2 parts;

[0217] Water, 75 parts;

[0218] Wherein, aminopyrimidine is 2-aminopyrimidine;

[0219] Wherein, the epoxy resin is epoxy resin E20;

[0220] Wherein, the silane coupling agent is y-aminopropyltriethoxysilane;

[0221] Wherein, the copper oxide is copper oxide modified by y-aminopropyltriethoxysilane;

[0222] Wherein, the polyaldehyde is glutaraldehyde and adipaldehyde in a weight ratio of 1:1;

[0223] The method for preparing the above-mentioned graphene conductive slurry comprises the following steps:

[0224] S1, under a protective atmosphere, mixing 2-aminopyrimidine and graphene in water, adjusting the pH to 8, and stirring at 2° C. for 24 hours, and obtaining a first modified graphene after centrifugal drying;

[0225] S2: preparing a polyaldehyde solution with a total molar concentration of 3% of the polyaldehyde, mixing the polyaldehyde solution with the first modified graphene at a molar ratio of 1:1, and obtaining a second modified graphene after centrifugation and drying;

[0226] S3: Add copper oxide to 50 mL of xylene, heat to 90°C, add y-aminopropyltriethoxysilane, heat to 115°C, stir for 6 hours, filter and dry to obtain modified copper oxide;

[0227] S4: Mix the modified copper oxide and water to obtain a copper oxide solution, add the second modified graphene, stir, add epoxy resin E20 and polyvinyl pyrrolidone to obtain a graphene conductive slurry.

[0228] Example 10

[0229] The difference between Example 10 and Example 3 is that the amount of raw materials used in the graphene conductive paste is different.

[0230] A graphene conductive slurry, the raw materials of which include the following components:

[0231] Graphene, 8 parts;

[0232] Aminopyrimidine, 0.5 part;

[0233] Epoxy resin, 20 parts;

[0234] Copper oxide, 5 parts;

[0235] Silane coupling agent, 0.4 parts;

[0236] Polyaldehyde, 8 parts;

[0237] Polyvinylpyrrolidone, 2 parts;

[0238] Water, 75 parts;

[0239] Wherein, aminopyrimidine is 2-aminopyrimidine;

[0240] Wherein, the epoxy resin is epoxy resin E20;

[0241] Wherein, the silane coupling agent is y-aminopropyltriethoxysilane;

[0242] Wherein, the copper oxide is copper oxide modified by y-aminopropyltriethoxysilane;

[0243] Wherein, the polyaldehyde is glutaraldehyde and adipaldehyde in a weight ratio of 1:1;

[0244] The method for preparing the above-mentioned graphene conductive slurry comprises the following steps:

[0245] S1, under a protective atmosphere, mixing 2-aminopyrimidine and graphene in water, adjusting the pH to 8, and stirring at 2° C. for 24 hours, and obtaining a first modified graphene after centrifugal drying;

[0246] S2: preparing a polyaldehyde solution with a total molar concentration of 3% of the polyaldehyde, mixing the polyaldehyde solution with the first modified graphene at a molar ratio of 1:1, and obtaining a second modified graphene after centrifugation and drying;

[0247] S3: Add copper oxide to 50 mL of xylene, heat to 90°C, add y-aminopropyltriethoxysilane, heat to 115°C, stir for 6 hours, filter and dry to obtain modified copper oxide;

[0248] S4: Mix the modified copper oxide and water to obtain a copper oxide solution, add the second modified graphene, stir, add epoxy resin E20 and polyvinyl pyrrolidone to obtain a graphene conductive slurry.

[0249] Embodiment 11

[0250] The difference between Example 11 and Example 3 is that the amount of raw materials used in the graphene conductive paste is different.

[0251] A graphene conductive slurry, the raw materials of which include the following components:

[0252] Graphene, 16 parts;

[0253] Aminopyrimidine, 1.2 parts;

[0254] Epoxy resin, 20 parts;

[0255] Copper oxide, 3 parts;

[0256] Silane coupling agent, 0.3 parts;

[0257] Polyaldehyde, 10 parts;

[0258] Polyvinylpyrrolidone, 2 parts;

[0259] Water, 75 parts;

[0260] Wherein, aminopyrimidine is 2-aminopyrimidine;

[0261] Wherein, the epoxy resin is epoxy resin E20;

[0262] Wherein, the silane coupling agent is y-aminopropyltriethoxysilane;

[0263] Wherein, the copper oxide is copper oxide modified by y-aminopropyltriethoxysilane;

[0264] Wherein, the polyaldehyde is glutaraldehyde and adipaldehyde in a weight ratio of 1:1;

[0265] The method for preparing the above-mentioned graphene conductive slurry comprises the following steps:

[0266] S1, under a protective atmosphere, mixing 2-aminopyrimidine and graphene in water, adjusting the pH to 8, and stirring at 2° C. for 24 hours, and obtaining a first modified graphene after centrifugal drying;

[0267] S2: preparing a polyaldehyde solution with a total molar concentration of 3% of the polyaldehyde, mixing the polyaldehyde solution with the first modified graphene at a molar ratio of 1:1, and obtaining a second modified graphene after centrifugation and drying;

[0268] S3: Add copper oxide to 50 mL of xylene, heat to 90°C, add y-aminopropyltriethoxysilane, heat to 115°C, stir for 6 hours, filter and dry to obtain modified copper oxide;

[0269] S4: Mix the modified copper oxide and water to obtain a copper oxide solution, add the second modified graphene, stir, add epoxy resin E20 and polyvinyl pyrrolidone to obtain a graphene conductive slurry.

[0270] Example 12

[0271] The difference between Example 12 and Example 3 is that the amount of raw materials used in the graphene conductive paste is different.

[0272] A graphene conductive slurry, the raw materials of which include the following components:

[0273] Graphene, 15 parts;

[0274] Aminopyrimidine, 0.8 part;

[0275] Epoxy resin, 25 parts;

[0276] Copper oxide, 5 parts;

[0277] Silane coupling agent, 0.3 parts;

[0278] polyaldehyde, 9 parts;

[0279] Polyvinylpyrrolidone, 3 parts;

[0280] Water, 80 parts;

[0281] Wherein, aminopyrimidine is 2-aminopyrimidine;

[0282] Wherein, the epoxy resin is epoxy resin E20;

[0283] Wherein, the silane coupling agent is y-aminopropyltriethoxysilane;

[0284] Wherein, the copper oxide is copper oxide modified by y-aminopropyltriethoxysilane;

[0285] Wherein, the polyaldehyde is glutaraldehyde and adipaldehyde in a weight ratio of 1:1;

[0286] The method for preparing the above-mentioned graphene conductive slurry comprises the following steps:

[0287] S1, under a protective atmosphere, mixing 2-aminopyrimidine and graphene in water, adjusting the pH to 8, and stirring at 2° C. for 24 hours, and obtaining a first modified graphene after centrifugal drying;

[0288] S2: preparing a polyaldehyde solution with a total molar concentration of 3% of the polyaldehyde, mixing the polyaldehyde solution with the first modified graphene at a molar ratio of 1:1, and obtaining a second modified graphene after centrifugation and drying;

[0289] S3: Add copper oxide to 50 mL of xylene, heat to 90°C, add y-aminopropyltriethoxysilane, heat to 115°C, stir for 6 hours, filter and dry to obtain modified copper oxide;

[0290] S4: Mix the modified copper oxide and water to obtain a copper oxide solution, add the second modified graphene, stir, add epoxy resin E20 and polyvinyl pyrrolidone to obtain a graphene conductive slurry.

[0291] Comparative Example 1

[0292] The difference between Comparative Example 1 and Example 3 is that the raw material of the graphene conductive paste of Comparative Example 1 does not contain aminopyrimidine.

[0293] A graphene conductive slurry, the raw materials of which include the following components:

[0294] Graphene, 8 parts;

[0295] Epoxy resin, 20 parts;

[0296] Copper oxide, 3 parts;

[0297] Silane coupling agent, 0.3 parts;

[0298] Polyaldehyde, 8 parts;

[0299] Polyvinylpyrrolidone, 2 parts;

[0300] Water, 75 parts;

[0301] Wherein, the epoxy resin is epoxy resin E20;

[0302] Wherein, the silane coupling agent is y-aminopropyltriethoxysilane;

[0303] Wherein, the copper oxide is copper oxide modified by y-aminopropyltriethoxysilane;

[0304] Wherein, the polyaldehyde is glutaraldehyde and adipaldehyde in a weight ratio of 1:1;

[0305] The method for preparing the above-mentioned graphene conductive slurry comprises the following steps:

[0306] S1: preparing a polyaldehyde solution with a total molar concentration of 3% of the polyaldehyde, mixing the polyaldehyde solution with graphene in a molar ratio of 1:1, and obtaining modified graphene after centrifugation and drying;

[0307] S2: Add copper oxide to 50 mL of xylene, heat to 90°C, add y-aminopropyltriethoxysilane, heat to 115°C, stir for 6 hours, filter and dry to obtain modified copper oxide;

[0308] S3: Mix the modified copper oxide and water to obtain a copper oxide solution, add the modified graphene, stir, add epoxy resin E20 and polyvinyl pyrrolidone to obtain a graphene conductive slurry.

[0309] Comparative Example 2

[0310] The difference between Comparative Example 2 and Example 3 is that in the raw material of the graphene conductive paste of Comparative Example 2, aminopyrimidine is replaced by aminopyrrole.

[0311] A graphene conductive slurry, the raw materials of which include the following components:

[0312] Graphene, 8 parts;

[0313] Aminopyrrole, 0.5 part;

[0314] Epoxy resin, 20 parts;

[0315] Copper oxide, 3 parts;

[0316] Silane coupling agent, 0.3 parts;

[0317] Polyaldehyde, 8 parts;

[0318] Polyvinylpyrrolidone, 2 parts;

[0319] Water, 75 parts;

[0320] wherein the aminopyrrole is 2-aminopyrrole;

[0321] Wherein, the epoxy resin is epoxy resin E20;

[0322] Wherein, the silane coupling agent is y-aminopropyltriethoxysilane;

[0323] Wherein, the copper oxide is copper oxide modified by y-aminopropyltriethoxysilane;

[0324] Wherein, the polyaldehyde is glutaraldehyde and adipaldehyde in a weight ratio of 1:1;

[0325] The method for preparing the above-mentioned graphene conductive slurry comprises the following steps:

[0326] S1, under a protective atmosphere, mixing 2-aminopyrrole and graphene in water, adjusting the pH to 8, and stirring at 2° C. for 24 h, and obtaining a first modified graphene after centrifugal drying;

[0327] S2: preparing a polyaldehyde solution with a total molar concentration of 3% of the polyaldehyde, mixing the polyaldehyde solution with the first modified graphene at a molar ratio of 1:1, and obtaining a second modified graphene after centrifugation and drying;

[0328] S3: Add copper oxide to 50 mL of xylene, heat to 90°C, add y-aminopropyltriethoxysilane, heat to 115°C, stir for 6 hours, filter and dry to obtain modified copper oxide;

[0329] S4: Mix the modified copper oxide and water to obtain a copper oxide solution, add the second modified graphene, stir, add epoxy resin E20 and polyvinyl pyrrolidone to obtain a graphene conductive slurry.

[0330] Comparative Example 3

[0331] The difference between Comparative Example 3 and Example 3 is that the raw material of the graphene conductive paste of Comparative Example 1 does not contain metal oxide.

[0332] A graphene conductive slurry, the raw materials of which include the following components:

[0333] Graphene, 8 parts;

[0334] Aminopyrimidine, 0.5 part;

[0335] Epoxy resin, 20 parts;

[0336] Polyaldehyde, 8 parts;

[0337] Polyvinylpyrrolidone, 2 parts;

[0338] Water, 75 parts;

[0339] Wherein, aminopyrimidine is 2-aminopyrimidine;

[0340] Wherein, the epoxy resin is epoxy resin E20;

[0341] Wherein, the polyaldehyde is glutaraldehyde and adipaldehyde in a weight ratio of 1:1;

[0342] The method for preparing the above-mentioned graphene conductive slurry comprises the following steps:

[0343] S1, under a protective atmosphere, mixing 2-aminopyrimidine and graphene in water, adjusting the pH to 8, and stirring at 2° C. for 24 hours, and obtaining a first modified graphene after centrifugal drying;

[0344] S2: preparing a polyaldehyde solution with a total molar concentration of 3% of the polyaldehyde, mixing the polyaldehyde solution with the first modified graphene at a molar ratio of 1:1, and obtaining a second modified graphene after centrifugation and drying;

[0345] S3: mixing the second modified graphene, epoxy resin E20 and polyvinyl pyrrolidone in water to obtain a graphene conductive slurry.

[0346] Performance Testing:

[0347] The performance of the graphene conductive pastes prepared in Examples 1-5 and Comparative Examples 1-3 was tested in the following manner. The test results are shown in Table 1.

[0348] Electrochemical test: After the graphene slurry is evenly dispersed, it is coated with an automatic coating machine. The film thickness is 50μm. After drying, the conductivity of the dry film is tested with a four-probe.

[0349] Adhesion test: The graphene slurry is prepared into an electroplating solution by a general method and used for hole metallization of the PCB board. The substrate is placed in the prepared electroplating solution and the current density is 10A / dm 2 The electroplating is carried out by turning on the power. The bottom blowing of air is used for stirring during the electroplating process. After the trough, grinding, anti-oxidation and drying, the coating is obtained. The adhesion of the coating is tested. The adhesion is expressed by the peel strength. The greater the peel strength, the greater the adhesion.

[0350] Table 1

[0351]

[0352]

[0353] As shown in Table 1, the slurry of Example 1 does not contain polyaldehyde, and cannot form an effective cross-linking network, nor can it form a "trap" structure to capture metal oxides. Therefore, the conductivity of the slurry and the adhesion of the coating are not as good as those of Example 3; the copper oxide in the slurry of Example 2 is not modified, and the agglomeration of a large amount of copper oxide accumulated in the "trap" cannot be avoided, and it cannot be connected with the epoxy resin through chemical bonds, so the effect is not as good as that of Example 3; the polyaldehyde in the slurry of Examples 4-5 is glutaraldehyde or adipic dialdehyde. Although a longer polyaldehyde is selected, a plurality of polyaldehydes with different lengths and structures are not selected, which cannot make The local tension of graphene is uneven, so the "trap" structure formed is not good; the slurry in Comparative Example 1 does not contain aminopyrimidine, and there is agglomeration between the graphene sheets, which has a great impact on the performance; the slurry component in Comparative Example 2 replaces aminopyrimidine with aminopyrrole relative to Example 3. On the one hand, the dinitrogen structure of aminopyrimidine gives it higher polarity and stronger hydrogen bonding force, and more polar functional groups can be introduced on the graphene surface. On the other hand, the nitrogen-containing heterocyclic structure of aminopyrimidine is more stable than aminopyrrole, which can better improve the stability of graphene; the slurry component in Comparative Example 3 does not contain metal oxides, so the conductivity is relatively poor.

[0354] The above are only embodiments of the present invention, and are not intended to limit the patent scope of the present invention. Any equivalent transformations made using the contents of the present invention specification, or directly or indirectly applied in related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A graphene conductive slurry, characterized in that: The raw materials of the graphene conductive slurry include the following components: Graphene; aminopyrimidine; Epoxy resin; Metal oxides; Solvent.

2. The graphene conductive paste according to claim 1, characterized in that: The raw materials of the graphene conductive slurry include the following components in parts by weight: Graphene, 8-20 parts; Aminopyrimidine, 0.5-2 parts; Epoxy resin, 20-30 parts; Copper oxide, 3-8 parts; Solvent, 75-85 parts.

3. The graphene conductive paste according to claim 1, characterized in that: The aminopyrimidine includes at least one of 4-aminopyrimidine and 2-aminopyrimidine.

4. The graphene conductive paste according to claim 1, characterized in that: The raw materials of the graphene conductive paste also include: polyaldehyde.

5. The graphene conductive paste according to claim 4, characterized in that: The polyaldehyde is a polyaldehyde having 3 or more carbon atoms.

6. The graphene conductive paste according to claim 1, characterized in that: The metal oxide includes copper oxide, and the copper oxide includes copper oxide modified by a silane coupling agent.

7. The graphene conductive paste according to claim 6, characterized in that: The method for preparing the copper oxide modified by the silane coupling agent comprises the following steps: mixing copper oxide, xylene and a silane coupling agent, and subjecting the mixture to a heating treatment to obtain the copper oxide modified by the silane coupling agent.

8. A method for preparing a graphene conductive slurry according to any one of claims 1 to 7, characterized in that: The following steps are involved: S1, under a protective atmosphere, mixing aminopyrimidine, graphene and a solvent to obtain a first modified graphene through reaction; S2: mixing the first modified graphene, epoxy resin and metal oxide to obtain the graphene conductive slurry.

9. The method according to claim 8, characterized in that: Step S2 also includes the following steps: mixing the first modified graphene with a polyaldehyde to obtain a second modified graphene, and then mixing the second modified graphene with an epoxy resin and a metal oxide.

10. A PCB board, characterized in that: The PCB board includes the graphene conductive paste as described in any one of claims 1 to 7.

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