An AGM type start-stop lead-carbon battery plate based on graphene carbon material and its preparation method

Abstract

The present invention relates to an AGM type start-stop lead-carbon battery plate based on graphene carbon material and a preparation method thereof. The AGM type start-stop lead-carbon battery plate based on graphene carbon material comprises the following raw materials in parts by weight: 100-150 parts of graphene substrate and 300-400 parts of nano-intercalation liquid. The preparation method of the AGM type start-stop lead-carbon battery plate based on graphene carbon material comprises the following steps: S1: Prepare the graphene substrate and the nano-intercalation liquid; S2: Apply the nano-intercalation liquid to the surface of the graphene substrate, and then perform a drying treatment to obtain the AGM type start-stop lead-carbon battery plate based on graphene carbon material. The AGM type start-stop lead-carbon battery plate based on graphene carbon material prepared by the present invention has an environmentally friendly, simple and reliable process, and has good mechanical properties and electrochemical properties.

Description

Technical Field

[0001] The present invention relates to the technical field of fuel cells, and particularly relates to an AGM type start-stop lead-carbon battery plate based on graphene carbon material and a preparation method thereof. Background Art

[0002] Fuel cell plates should not only play a role in conducting between individual cells, but also separate oxidants and reductants. In addition, the battery plates also need to have good heat conduction and heat dissipation capabilities, as well as a certain strength required to support the membrane electrode. The plate materials mainly include graphite material types, metal material types, and composite material types. Among them, composite plates are mainly made of graphite powder, carbon powder, and resin, and are obtained by adding metal materials, carbon fibers, and ceramic fibers. In the existing fuel cell composite plates, there are generally problems such as poor dispersibility and binding property of carbon-based materials such as graphene in the resin, resulting in disadvantages such as poor mechanical properties, large internal resistance, and poor thermal stability of the composite plates. At the same time, the traditional preparation process is complex and costly, making it difficult to meet the needs of industry development. Summary of the Invention

[0003] In view of this, the purpose of the present invention is to provide an AGM type start-stop lead-carbon battery plate based on graphene carbon material and a manufacturing method thereof, with an environmentally friendly, simple, and reliable process, and having good mechanical properties and electrochemical properties.

[0004] In order to achieve the above purpose, the present invention provides the following technical solutions:

[0005] An AGM type start-stop lead-carbon battery plate based on graphene carbon material, comprising the following raw materials in parts by weight: 100 - 150 parts of graphene substrate and 300 - 400 parts of nano-intercalation liquid.

[0006] A preparation method of an AGM type start-stop lead-carbon battery plate based on graphene carbon material, comprising the following steps:

[0007] S1: Prepare a graphene substrate and a nano-intercalation liquid;

[0008] S2: Apply the nano-intercalation liquid to the surface of the graphene substrate, and then perform a drying treatment to obtain an AGM type start-stop lead-carbon battery plate based on graphene carbon material.

[0009] Preferably, the preparation method of the graphene substrate in the step S1 is specifically as follows:

[0010] S11: Prepare a modified graphene oxide solution and a modified metal salt solution;

[0011] S12: Mix lead powder, lignin, the modified metal salt solution, and the modified graphene oxide solution evenly, heat at 150 - 200 °C for 10 - 16 h, then add them to a mold, apply pressure to form and keep warm to obtain a graphene substrate.

[0012] Preferably, in the step S12, the weight ratio of lead powder, lignin, modified metal salt solution and modified graphene oxide solution is 3:1:2:2.

[0013] Preferably, the preparation method of the modified graphene oxide in the step S11 is specifically as follows:

[0014] S111: Amidation of graphene oxide: Mix a silane coupling agent, graphene oxide and an ethanol solution with a volume fraction of 50%, and stir and react at 60-80°C for 12-24h to obtain an amidated graphene oxide solution;

[0015] Acidification of carbon fiber: Mix carbon fiber, concentrated sulfuric acid with a volume fraction of 75% and concentrated hydrochloric acid with a volume fraction of 75%, stir and react at 60-80°C for 4-6h, and then dry at 80-100°C for 12-24h to obtain acidified carbon fiber;

[0016] S112: Mix the acidified carbon fiber with the amidated graphene oxide solution and stir for 12-24h to obtain a modified graphene oxide solution.

[0017] Preferably, in the step S111, the weight ratio of the silane coupling agent, graphene oxide and ethanol solution is 1:2:5; the weight ratio of carbon fiber, concentrated sulfuric acid and concentrated hydrochloric acid is 1:2:2;

[0018] In the step S112, the weight ratio of the acidified carbon fiber to the amidated graphene oxide solution is 1:1.

[0019] Preferably, the preparation method of the modified metal salt solution in the step S11 is specifically as follows:

[0020] Mix titanium dioxide, polyvinyl alcohol, chitosan, glacial acetic acid with a volume fraction of 75% and a metal salt solution with a mass fraction of 75%, and stir for 12-24h to obtain a modified metal salt solution.

[0021] Preferably, the weight ratio of titanium dioxide, polyvinyl alcohol, chitosan, glacial acetic acid and metal salt solution is 1:1:1:3:5;

[0022] The metal salt solution is one or more of manganese sulfate solution, lead nitrate solution and nickel nitrate solution.

[0023] Preferably, the preparation method of the nano-intercalation liquid in the step S2 is specifically as follows:

[0024] Mix carbon black particles, nano-aluminum oxide, polyvinylpyrrolidone and ethanol with a volume fraction of 75%, and stir for 1-2h to obtain a nano-intercalation liquid.

[0025] Preferably, the weight ratio of the carbon black particles, nano-aluminum oxide, polyvinylpyrrolidone, and ethanol is 1:1:1:2.

[0026] In the present invention, the amino-functionalized graphene oxide and acidified carbon fiber are combined through zwitterionic interaction to form a multi-scale reinforcement, enabling a more stable loading of graphene oxide on the fiber surface. At the same time, the degree of surface disorder of the carbon fiber modified by graphene oxide increases, which can enhance the flexibility of the molecular chain, improve the binding ability with lead powder, lignin, and modified metal salt solution, and also improve the mechanical properties and toughness of the substrate.

[0027] In the present invention, after modifying the metal salt solution with chitosan, not only the loading capacity of the metal salt particles is improved, but also it is more conducive to the adsorption of the metal salt particles on the surface of the multi-scale reinforcement formed by amino-functionalized graphene oxide and acidified carbon fiber.

[0028] After the nano-intercalation liquid of the present invention is modified with polyvinylpyrrolidone, the carbon black-aluminum oxide nanoparticles exist in the form of small aggregates, having good dispersibility and good particle binding force. At the same time, the nano-hollow porous structure of carbon black-aluminum oxide has a large specific surface area, which can form a connected network structure on the surface and inside of the graphene substrate, facilitating the rapid conduction of electrons on the surface and inside of the graphene substrate and improving the conductivity of the substrate. Specific Embodiments

[0029] The technical solutions in the embodiments of the present invention are clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of them. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work belong to the scope of protection of the present invention. Additionally, it should be particularly noted that the raw materials and equipment of the present invention can be obtained commercially and will not be listed one by one. Example 1:

[0030] An AGM type start-stop lead-carbon battery plate based on graphene carbon material, comprising the following raw materials in parts by weight: 150 parts of graphene substrate and 400 parts of nano-intercalation liquid.

[0031] A preparation method of an AGM type start-stop lead-carbon battery plate based on graphene carbon material, comprising the following steps:

[0032] S1: Prepare the graphene substrate:

[0033] S11: Prepare the modified graphene oxide solution:

[0034] S111: Amidation of graphene oxide: Mix a silane coupling agent, graphene oxide, and an ethanol solution with a volume fraction of 50%, and stir and react at 80 °C for 24 h to obtain an amidated graphene oxide solution; among them, the weight ratio of the silane coupling agent, graphene oxide, and ethanol solution is 1:2:5;

[0035] Acidification of carbon fiber: Mix carbon fiber, concentrated sulfuric acid with a volume fraction of 75%, and concentrated hydrochloric acid with a volume fraction of 75%, stir and react at 80 °C for 6 h, and then dry at 100 °C for 24 h to obtain acidified carbon fiber; among them, the weight ratio of carbon fiber, concentrated sulfuric acid, and concentrated hydrochloric acid is 1:2:2;

[0036] S112: Mix the acidified carbon fiber and the amidated graphene oxide solution in a weight ratio of 1:1, and stir for 12 - 24 h to obtain a modified graphene oxide solution;

[0037] Preparation of modified metal salt solution: Mix titanium dioxide, polyvinyl alcohol, chitosan, glacial acetic acid with a volume fraction of 75%, and a metal salt solution with a mass fraction of 75%, and stir for 24 h to obtain a modified metal salt solution; among them, the weight ratio of titanium dioxide, polyvinyl alcohol, chitosan, glacial acetic acid, and metal salt solution is 1:1:1:3:5; the metal salt solution is one or more of a manganese sulfate solution, a lead nitrate solution, and a nickel nitrate solution;

[0038] S12: Mix lead powder, lignin, the above-mentioned modified metal salt solution, and the above-mentioned modified graphene oxide solution evenly, heat at 200 °C for 16 h, then add them to a mold, and under the conditions of a temperature of 150 °C and a pressure of 60 MPa, press and form to obtain a graphene substrate; among them, the weight ratio of lead powder, lignin, modified metal salt solution, and modified graphene oxide solution is 3:1:2:2;

[0039] Preparation of nano-intercalation liquid: Mix carbon black particles, nano-aluminum oxide, polyvinylpyrrolidone, and ethanol with a volume fraction of 75%, and stir for 2 h to obtain a nano-intercalation liquid; among them, the weight ratio of carbon black particles, nano-aluminum oxide, polyvinylpyrrolidone, and ethanol is 1:1:1:2;

[0040] S2: Apply the nano-intercalation liquid to the surface of the graphene substrate, and then perform a drying treatment to obtain an AGM type start-stop lead-carbon battery plate based on graphene carbon material. Example two:

[0041] An AGM type start-stop lead-carbon battery plate based on graphene carbon material, comprising the following raw materials in parts by weight: 100 parts of graphene substrate and 300 parts of nano-intercalation liquid.

[0042] A preparation method of an AGM type start-stop lead-carbon battery plate based on graphene carbon material, comprising the following steps:

[0043] S1: Preparation of graphene substrate:

[0044] S11: Preparation of modified graphene oxide solution:

[0045] S111: Amidation of graphene oxide: Mix silane coupling agent, graphene oxide and ethanol solution with a volume fraction of 50%, and stir and react at 60 °C for 12 h to obtain amidated graphene oxide solution; wherein, the weight ratio of silane coupling agent, graphene oxide and ethanol solution is 1:2:5;

[0046] Acidify carbon fiber: Mix carbon fiber, concentrated sulfuric acid with a volume fraction of 75% and concentrated hydrochloric acid with a volume fraction of 75%, stir and react at 60 °C for 4 h, and then dry at 80 °C for 12 h to obtain acidified carbon fiber; wherein, the weight ratio of carbon fiber, concentrated sulfuric acid and concentrated hydrochloric acid is 1:2:2;

[0047] S112: Mix acidified carbon fiber and amidated graphene oxide solution according to a weight ratio of 1:1, and stir for 12 h to obtain modified graphene oxide solution;

[0048] Preparation of modified metal salt solution: Mix titanium dioxide, polyvinyl alcohol, chitosan, glacial acetic acid with a volume fraction of 75% and metal salt solution with a mass fraction of 75%, and stir for 12 h to obtain modified metal salt solution; wherein, the weight ratio of titanium dioxide, polyvinyl alcohol, chitosan, glacial acetic acid and metal salt solution is 1:1:1:3:5; the metal salt solution is one or more of manganese sulfate solution, lead nitrate solution and nickel nitrate solution;

[0049] S12: Mix lead powder, lignin, the above-mentioned modified metal salt solution and the above-mentioned modified graphene oxide solution evenly, heat at 150 °C for 10 h, then add it into a mold, and under the conditions of a temperature of 150 °C and a pressure of 60 MPa, after pressure molding, obtain a graphene substrate; wherein, the weight ratio of lead powder, lignin, modified metal salt solution and modified graphene oxide solution is 3:1:2:2;

[0050] Preparation of nano-intercalation liquid: Mix carbon black particles, nano-aluminum oxide, polyvinylpyrrolidone and ethanol with a volume fraction of 75%, and stir for 1 h to obtain nano-intercalation liquid; wherein, the weight ratio of carbon black particles, nano-aluminum oxide, polyvinylpyrrolidone and ethanol is 1:1:1:2;

[0051] S2: Apply the nano-intercalation liquid to the surface of the graphene substrate, and then carry out drying treatment to obtain an AGM type start-stop lead-carbon battery plate based on graphene carbon material. Example three:

[0052] An AGM type start-stop lead-carbon battery plate based on graphene carbon material, comprising the following raw materials in parts by weight: 120 parts of graphene substrate and 350 parts of nano-intercalation liquid.

[0053] A preparation method of an AGM type start-stop lead-carbon battery plate based on graphene carbon material, comprising the following steps:

[0054] S1: Prepare graphene substrate:

[0055] S11: Prepare modified graphene oxide solution:

[0056] S111: Amination of graphene oxide: Mix silane coupling agent, graphene oxide and ethanol solution with a volume fraction of 50%, stir and react at 70 °C for 18 h to obtain aminated graphene oxide solution; wherein, the weight ratio of silane coupling agent, graphene oxide and ethanol solution is 1:2:5;

[0057] Acidify carbon fiber: Mix carbon fiber, concentrated sulfuric acid with a volume fraction of 75% and concentrated hydrochloric acid with a volume fraction of 75%, stir and react at 70 °C for 5 h, then dry at 90 °C for 18 h to obtain acidified carbon fiber; wherein, the weight ratio of carbon fiber, concentrated sulfuric acid and concentrated hydrochloric acid is 1:2:2;

[0058] S112: Mix the acidified carbon fiber and the aminated graphene oxide solution according to a weight ratio of 1:1, stir for 18 h to obtain a modified graphene oxide solution;

[0059] Prepare modified metal salt solution: Mix titanium dioxide, polyvinyl alcohol, chitosan, glacial acetic acid with a volume fraction of 75% and metal salt solution with a mass fraction of 75%, stir for 18 h to obtain a modified metal salt solution; wherein, the weight ratio of titanium dioxide, polyvinyl alcohol, chitosan, glacial acetic acid and metal salt solution is 1:1:1:3:5; the metal salt solution is one or more of manganese sulfate solution, lead nitrate solution and nickel nitrate solution;

[0060] S12: Mix lead powder, lignin, the above-mentioned modified metal salt solution and the above-mentioned modified graphene oxide solution evenly, heat at 180 °C for 12 h, then add to a mold, and under the conditions of a temperature of 150 °C and a pressure of 60 MPa, press and form to obtain a graphene substrate; wherein, the weight ratio of lead powder, lignin, modified metal salt solution and modified graphene oxide solution is 3:1:2:2;

[0061] Prepare nano-intercalation liquid: Mix carbon black particles, nano-aluminum oxide, polyvinylpyrrolidone and ethanol with a volume fraction of 75%, stir for 1.5 h to obtain nano-intercalation liquid; wherein, the weight ratio of carbon black particles, nano-aluminum oxide, polyvinylpyrrolidone and ethanol is 1:1:1:2;

[0062] S2: Apply the nano-intercalation solution to the surface of the graphene substrate, and then perform a drying treatment to obtain the AGM type start-stop lead-carbon battery plate based on the graphene carbon material.

[0063] Comparative Example 1:

[0064] Comparative Example 1 is basically the same as Example 1 in terms of the component weight parts and the preparation method. The difference is that the metal salt solution is not modified. Specifically:

[0065] An AGM type start-stop lead-carbon battery plate based on the graphene carbon material, comprising the following raw materials in weight parts: 150 parts of graphene substrate and 400 parts of nano-intercalation solution.

[0066] A preparation method of an AGM type start-stop lead-carbon battery plate based on the graphene carbon material, comprising the following steps:

[0067] S1: Prepare the graphene substrate:

[0068] S11: Prepare the modified graphene oxide solution:

[0069] S111: Amination of graphene oxide: Mix the silane coupling agent, graphene oxide and ethanol solution with a volume fraction of 50%, and stir and react at 80 °C for 24 h to obtain the aminated graphene oxide solution; among them, the weight part ratio of the silane coupling agent, graphene oxide and ethanol solution is 1:2:5;

[0070] Acidify carbon fiber: Mix carbon fiber, concentrated sulfuric acid with a volume fraction of 75% and concentrated hydrochloric acid with a volume fraction of 75%, stir and react at 80 °C for 6 h, and then dry at 100 °C for 24 h to obtain acidified carbon fiber; among them, the weight part ratio of carbon fiber, concentrated sulfuric acid and concentrated hydrochloric acid is 1:2:2;

[0071] S112: Mix the acidified carbon fiber and the aminated graphene oxide solution according to a weight part ratio of 1:1, and stir for 12 - 24 h to obtain the modified graphene oxide solution;

[0072] S12: Mix the lead powder, lignin, metal salt solution with a mass fraction of 75% and the above-mentioned modified graphene oxide solution evenly, heat at 200 °C for 16 h, then add it to the mold, and under the conditions of a temperature of 150 °C and a pressure of 60 MPa, after pressure molding, obtain the graphene substrate; among them, the weight part ratio of lead powder, lignin, metal salt solution and modified graphene oxide solution is 3:1:2:2, and the metal salt solution is one or several of manganese sulfate solution, lead nitrate solution and nickel nitrate solution;

[0073] Preparation of nano-intercalated liquid: Mix carbon black particles, nano-aluminum oxide, polyvinylpyrrolidone, and ethanol with a volume fraction of 75% and stir for 2 h to obtain the nano-intercalated liquid. Among them, the weight ratio of carbon black particles, nano-aluminum oxide, polyvinylpyrrolidone, and ethanol is 1:1:1:2;

[0074] S2: Apply the nano-intercalated liquid to the surface of the graphene substrate and then perform a drying treatment to obtain an AGM type start-stop lead-carbon battery plate based on graphene carbon material.

[0075] Comparative Example 2:

[0076] Comparative Example 2 is basically the same as Example 1 in terms of the component weight ratio and preparation method. The difference is that the graphene oxide solution is not modified and the nano-intercalated liquid is not included. Specifically:

[0077] An AGM type start-stop lead-carbon battery plate based on graphene carbon material, comprising the following raw materials in parts by weight: 150 parts of graphene substrate.

[0078] A preparation method of an AGM type start-stop lead-carbon battery plate based on graphene carbon material, comprising the following steps:

[0079] S1: Preparation of graphene substrate:

[0080] Preparation of modified metal salt solution: Mix titanium dioxide, polyvinyl alcohol, chitosan, glacial acetic acid with a volume fraction of 75%, and a metal salt solution with a mass fraction of 75% and stir for 24 h to obtain the modified metal salt solution. Among them, the weight ratio of titanium dioxide, polyvinyl alcohol, chitosan, glacial acetic acid, and metal salt solution is 1:1:1:3:5; the metal salt solution is one or more of manganese sulfate solution, lead nitrate solution, and nickel nitrate solution;

[0081] Preparation of graphene oxide solution: Mix graphene oxide and an ethanol solution with a volume fraction of 50% to obtain the graphene oxide solution. Among them, the weight ratio of graphene oxide and ethanol solution is 2:5;

[0082] S12: Mix lead powder, lignin, the above-mentioned modified metal salt solution, and graphene oxide solution evenly, heat at 200 °C for 16 h, then add them into a mold, and under the conditions of a temperature of 150 °C and a pressure of 60 MPa, after pressure forming, obtain the graphene substrate. Among them, the weight ratio of lead powder, lignin, modified metal salt solution, and graphene oxide solution is 3:1:2:2;

[0083] S2: Perform a drying treatment on the graphene substrate again to obtain an AGM type start-stop lead-carbon battery plate based on graphene carbon material.

[0084] The bending strength and conductivity of the battery plates obtained in Examples 1-3 and Comparative Examples 1-2 were tested according to GB / T 20042.6-2011, and the results are shown in Table 1.

[0085] Table 1

[0086]

[0087] As can be seen from the above table, the bending strength and conductivity of Examples 1-3 are higher than those of Comparative Example 1 and Comparative Example 2, indicating that the battery plates of the present invention have good mechanical properties and electrochemical properties.

[0088] The above description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be obvious to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A preparation method of an AGM type start-stop lead-carbon battery plate based on graphene carbon material, characterized in that, It includes the following steps: S1: Prepare a graphene substrate and a nano-intercalation solution; S2: Apply the nano-intercalation solution to the surface of the graphene substrate, and then perform a drying treatment to obtain an AGM type start-stop lead-carbon battery plate based on graphene carbon material; The specific method for preparing the graphene substrate in step S1 is as follows: S11: Prepare a modified graphene oxide solution and a modified metal salt solution; S12: Mix lead powder, lignin, the modified metal salt solution and the modified graphene oxide solution evenly, heat at 150 - 200 °C for 10 - 16 h, then add them into a mold, press and form and keep warm to obtain a graphene substrate; The specific method for preparing the modified graphene oxide in step S11 is as follows: S111: Amino-functionalization of graphene oxide: Mix a silane coupling agent, graphene oxide and an ethanol solution with a volume fraction of 50%, stir and react at 60 - 80 °C for 12 - 24 h to obtain an amino-functionalized graphene oxide solution; Acidify carbon fiber: Mix carbon fiber, concentrated sulfuric acid with a volume fraction of 75% and concentrated hydrochloric acid with a volume fraction of 75%, stir and react at 60 - 80 °C for 4 - 6 h, then dry at 80 - 100 °C for 12 - 24 h to obtain acidified carbon fiber; S112: Mix the acidified carbon fiber with the amino-functionalized graphene oxide solution and stir for 12 - 24 h to obtain a modified graphene oxide solution; The specific method for preparing the modified metal salt solution in step S11 is as follows: Mix titanium dioxide, polyvinyl alcohol, chitosan, glacial acetic acid with a volume fraction of 75% and a metal salt solution with a mass fraction of 75%, stir for 12 - 24 h to obtain a modified metal salt solution; The metal salt solution is one or more of a manganese sulfate solution, a lead nitrate solution and a nickel nitrate solution; The specific method for preparing the nano-intercalation solution in step S2 is as follows: Mix carbon black particles, nano-aluminum oxide, polyvinylpyrrolidone and ethanol with a volume fraction of 75%, stir for 1 - 2 h to obtain a nano-intercalation solution.

2. The preparation method of the AGM type start-stop lead-carbon battery plate based on graphene carbon material according to claim 1, characterized in that, In step S12, the weight ratio of lead powder, lignin, the modified metal salt solution and the modified graphene oxide solution is 3:1:2:

2.

3. The preparation method of the AGM type start-stop lead-carbon battery plate based on graphene carbon material according to claim 1, characterized in that, In step S111, the weight ratio of the silane coupling agent, graphene oxide and the ethanol solution is 1:2:5; the weight ratio of carbon fiber, concentrated sulfuric acid and concentrated hydrochloric acid is 1:2:2; In step S112, the weight ratio of the acidified carbon fiber to the amino-functionalized graphene oxide solution is 1:

1.

4. The preparation method of the AGM type start-stop lead-carbon battery plate based on graphene carbon material according to claim 1, characterized in that, The weight ratio of titanium dioxide, polyvinyl alcohol, chitosan, glacial acetic acid and the metal salt solution is 1:1:1:3:

5.

5. The preparation method of the AGM type start-stop lead-carbon battery plate based on graphene carbon material according to claim 1, characterized in that, The weight ratio of carbon black particles, nano-aluminum oxide, polyvinylpyrrolidone and ethanol is 1:1:1:

2.

6. An AGM type start-stop lead-carbon battery plate based on graphene carbon material, which is made by the preparation method described in claim 1, is characterized in that, It includes raw materials in the following weight parts: 100 - 150 parts of graphene substrate and 300 - 400 parts of nano-intercalation solution.

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