A porous polymer hydrogen storage material and preparation method thereof

Abstract

The present invention relates to the field of C08G61 / 00, and specifically relates to a porous polymer hydrogen storage material and a preparation method thereof. The porous polymer hydrogen storage material comprises 80-100 parts of a cross-linked porous polymer, 10-20 parts of a metal compound, 1-5 parts of an amine compound, 1-3 parts of a porogen, 1-5 parts of a solvent, and 10-20 parts of water. The porous polymer hydrogen storage material has high hydrogen storage capacity and high stability, has a high specific surface area and pore volume, high pore structure retention, and low hydrogen adsorption enthalpy, thereby avoiding the problem of high hydrogen desorption temperature caused by the use of metal hydride hydrogen storage materials in the prior art, and provides new ideas and methods for the development of hydrogen storage materials and the subsequent application of hydrogen storage technologies.

Description

Technical Field

[0001] The present invention relates to the field of C08G61 / 00, and in particular to a porous polymer hydrogen storage material and a preparation method thereof. Background Art

[0002] As a pollution-free, clean and renewable energy source, the development and application of hydrogen energy has received widespread attention from various countries. Among them, the development and application of hydrogen storage technology and hydrogen storage materials are the key links in realizing the development and utilization of hydrogen energy.

[0003] Currently, high-pressure oxygen storage and liquefied argon storage in practical applications require high-quality hydrogen storage containers, and there are problems with safety and high cost. Metal hydrides as hydrogen storage materials have problems with high hydrogen release temperatures and poor hydrogen release kinetics. Polymer materials with porous properties have attracted considerable attention. Chinese patent CN104558515A discloses a method for preparing a porous polymer, which mainly involves mixing melamine with an aprotic solvent and then adding an MDI trimer to prepare the porous polymer. The polymer is then used for hydrogen adsorption, but high hydrogen adsorption capacity must be achieved under high pressure. Chinese patent CN106905526 discloses a rigid skeleton porous polymer with gas adsorption properties, its preparation method, and application. It mainly uses monomer-substituted triaryl tricyanoimidazole under zinc chloride catalysis to provide a material with high nitrogen content and microporous structure. Although this improves adsorption efficiency to a certain extent, the pore structure retention is relatively low.

[0004] Therefore, a porous polymer hydrogen storage material with high hydrogen storage capacity and high stability is provided, which has a high specific surface area and pore volume, high pore structure retention, and low hydrogen adsorption enthalpy, avoiding the problem of high hydrogen desorption temperature caused by the use of metal hydride hydrogen storage materials in the existing technology, and providing new ideas and methods for the development of hydrogen storage materials and the subsequent application of hydrogen storage technology. Summary of the Invention

[0005] In order to solve the above problems, the present invention provides a porous polymer hydrogen storage material on the one hand. The raw materials for its preparation include at least 80-100 parts of cross-linked porous polymer, 10-20 parts of metal compound, 1-5 parts of amine compound, 1-3 parts of porogen, 1-5 parts of solvent and 10-20 parts of water, calculated by weight.

[0006] As a preferred technical solution, the raw materials for preparing the cross-linked porous polymer include at least 10-15 parts of aromatic compounds, 0.5-1.2 parts of cross-linking agents, 6-8 parts of functional additives, and 1-1.2 parts of 1,2-dichloroethane, by weight.

[0007] As a preferred technical solution, the aromatic compound is at least one of chloromethylated polystyrene and 4,4'-dichloromethyl-1,1'biphenyl; preferably, the aromatic compound is a combination of chloromethylated polystyrene and 4,4'-dichloromethyl-1,1'biphenyl; preferably, the mass ratio of the chloromethylated polystyrene and 4,4'-dichloromethyl-1,1'biphenyl is (0.5-1.2): (0.8-1.5);

[0008] The chloromethylated polystyrene was purchased from Guangzhou Weber Technology Co., Ltd.; the 4,4'-dichloromethyl-1,1'biphenyl was purchased from J&K Technology Co., Ltd.;

[0009] As a preferred technical solution, the cross-linking agent is selected from at least one of vinylbenzyl chloride, dichloromethylbenzene, monochlorodimethyl ether, and trichloromethyl mesitylene; preferably, the cross-linking agent is vinylbenzyl chloride;

[0010] As a preferred technical solution, the functional additive includes at least two of azobisisobutyronitrile, ferric chloride (FeCl3), and tin tetrachloride (SnCl4); preferably, the functional additive includes azobisisobutyronitrile, ferric chloride, and tin tetrachloride; the mass ratio of azobisisobutyronitrile, ferric chloride, and tin tetrachloride is (0.2-0.5): (3-5): (2-4);

[0011] As a preferred technical solution, the preparation method of the cross-linked porous polymer is as follows: under the condition of controlling the temperature at 50-60°C, adding an aromatic compound and 1,2-dichloroethane into a container and ultrasonically dispersing them for 30-40 minutes, raising the temperature to 60-70°C, adding a cross-linking agent and a functional additive under stirring conditions, controlling the speed at 200-300 rpm and stirring the reaction for 10-12 hours, and then centrifuging, washing, and drying to obtain the polymer.

[0012] Based on the system of the present invention, aromatic compounds are used as the main raw materials, and a cross-linked porous polymer is prepared by cross-linking with a cross-linking agent. The provided porous polymer hydrogen storage material has a low adsorption enthalpy when hydrogen adsorbs, avoiding the problem of excessively high hydrogen desorption temperature when metal hydrides are used as hydrogen storage materials in the prior art. Specifically, the cross-linked porous polymer in the present invention uses chloromethylated polystyrene and 4,4'-dichloromethyl-1,1'biphenyl as aromatic compounds in a mass ratio of (0.5-1.2): (0.8-1.5), and is cross-linked using vinylbenzyl chloride. The provided cross-linked porous polymer has a highly cross-linked rigid structure and a high specific surface area. Due to the special segment structure of vinylbenzyl chloride, the pore structure retention of the cross-linked porous polymer is greatly improved, thereby ensuring the comprehensive performance of the hydrogen storage material.

[0013] As a preferred technical solution, the porogen is polyethylene glycol; preferably, the weight average molecular weight of the polyethylene glycol is 200-400;

[0014] During the research process, the inventor unexpectedly discovered that when polyethylene glycol is introduced as a porogen into the hydrogen storage material system, the pore volume ratio of the self-prepared cross-linked porous polymer is further increased without affecting the rigid structure and comprehensive performance of the cross-linked porous polymer, thereby effectively increasing the hydrogen storage capacity.

[0015] As a preferred technical solution, the solvent is 1,2-dichloroethane;

[0016] As a preferred technical solution, the metal compound is selected from one or a combination of zirconium chloride, platinum chloride, cobalt chloride, and palladium chloride; preferably, the metal compound is zirconium chloride and palladium chloride; the mass ratio of zirconium chloride to palladium chloride is (4-6): (0.8-1.5).

[0017] As a preferred technical solution, the amine compound is selected from at least one of dopamine, diphenylamine, oleylamine, and polyaniline; preferably, the amine compound is dopamine.

[0018] During the experimental exploration process, the present application found that on the basis of a self-prepared cross-linked porous polymer, by introducing a metal compound combination of zirconium chloride and palladium chloride in a mass ratio of (4-6): (0.8-1.5), especially using dopamine as a medium for bonding between the metal compound and the cross-linked porous polymer, the metal is effectively introduced into the cross-linked porous polymer structure, so that the hydrogen storage capacity and structural stability of the provided porous polymer hydrogen storage material are further improved, and the hydrogen storage capacity is increased under low pressure conditions. The inventor speculates that the reason may be that the self-prepared cross-linked porous polymer has a high degree of pore structure retention under high cross-linking, and the high specific surface area and pore volume ratio are conducive to the introduction of metals. Under the bridging effect of dopamine, the metal zirconium and palladium in the system are effectively introduced and fixed in the cross-linked porous polymer structure, thereby improving the structural stability of the porous polymer hydrogen storage material. At a specific mass ratio, a synergistic effect is exerted, and the hydrogen storage and dehydrogenation cycle stability is improved through the "hydrogen overflow" mechanism, thereby enhancing the hydrogen storage performance of the material.

[0019] Another aspect of the present invention provides a method for preparing a porous polymer hydrogen storage material, comprising at least the following steps:

[0020] (1) Mixing the cross-linked porous polymer and the solvent by weight at 50-60° C. with stirring, and ultrasonically dispersing, and then heating to 70-80° C. and adding the porogen to react to obtain a mixture A;

[0021] (2) stirring and mixing the metal compound, the amine compound, and water at 50-60° C., and ultrasonically dispersing the mixture for 10-20 minutes to obtain a mixture B;

[0022] (3) Adding mixture B to mixture A in an inert atmosphere, reacting at 60-80° C. for 8-12 hours to obtain a porous polymer mixture, filtering, washing, and drying under reduced pressure to obtain a porous polymer hydrogen storage material.

[0023] Beneficial effects:

[0024] 1. The present invention provides a porous polymer hydrogen storage material with high hydrogen storage capacity and high stability, which has a high specific surface area and pore volume, high pore structure retention, and low hydrogen adsorption enthalpy. It avoids the problem of high hydrogen desorption temperature caused by the use of metal hydride hydrogen storage materials in the existing technology, and provides new ideas and methods for the development of hydrogen storage materials and the subsequent application of hydrogen storage technology.

[0025] 2. Based on the system of the present invention, aromatic compounds are used as the main raw materials, and cross-linked porous polymers are prepared by cross-linking with a cross-linking agent, so that the provided porous polymer material hydrogen storage material has a low adsorption enthalpy when adsorbing hydrogen, avoiding the problem of excessively high hydrogen desorption temperature when using metal hydrides as hydrogen storage materials in the prior art.

[0026] 3. The cross-linked porous polymer in the present invention uses chloromethylated polystyrene and 4,4'-dichloromethyl-1,1'biphenyl as aromatic compounds in a mass ratio of (0.5-1.2): (0.8-1.5), and is cross-linked using vinylbenzyl chloride. The cross-linked porous polymer has a highly cross-linked rigid structure and a high specific surface area. Due to the special segment structure of vinylbenzyl chloride, the pore structure retention of the cross-linked porous polymer is greatly improved, thereby ensuring the comprehensive performance of the hydrogen storage material.

[0027] 4. The present invention introduces polyethylene glycol as a porogen into the hydrogen storage material system, which further increases the pore volume ratio of the self-prepared cross-linked porous polymer without affecting the rigid structure and comprehensive performance of the cross-linked porous polymer, thereby effectively increasing the hydrogen storage capacity.

[0028] 5. Based on the self-prepared cross-linked porous polymer, the present invention introduces a metal compound combination of zirconium chloride and palladium chloride in a mass ratio of (4-6): (0.8-1.5), and especially adopts dopamine as a medium for bonding between the metal compound and the cross-linked porous polymer, thereby effectively introducing the metal into the cross-linked porous polymer structure, thereby further improving the hydrogen storage capacity and structural stability of the provided porous polymer hydrogen storage material, and having an increased hydrogen storage capacity under low pressure conditions. DETAILED DESCRIPTION

[0029] Example 1

[0030] Example 1 of the present invention provides a porous polymer hydrogen storage material. On the one hand, the raw materials for its preparation include, by weight: 90 parts of cross-linked porous polymer, 15 parts of metal compound, 4 parts of amine compound, 2 parts of porogen, 4 parts of solvent and 15 parts of water.

[0031] The raw materials for preparing the cross-linked porous polymer include, by weight, 12 parts of aromatic compounds, 1 part of cross-linking agent, 7 parts of functional additives, and 1 part of 1,2-dichloroethane;

[0032] The aromatic compound is a combination of chloromethylated polystyrene and 4,4'-dichloromethyl-1,1'biphenyl; the mass ratio of the chloromethylated polystyrene to 4,4'-dichloromethyl-1,1'biphenyl is 1:1.2;

[0033] The chloromethylated polystyrene was purchased from Guangzhou Weber Technology Co., Ltd.; the 4,4'-dichloromethyl-1,1'biphenyl was purchased from J&K Technology Co., Ltd.;

[0034] The cross-linking agent is vinylbenzyl chloride;

[0035] The functional additives include azobisisobutyronitrile, ferric chloride, and tin tetrachloride; the mass ratio of azobisisobutyronitrile, ferric chloride, and tin tetrachloride is 0.3:4:3;

[0036] The preparation method of the cross-linked porous polymer is as follows: under the condition of controlling the temperature at 55°C, adding an aromatic compound and 1,2-dichloroethane into a container and ultrasonically dispersing them for 35 minutes, then raising the temperature to 65°C, adding a cross-linking agent and a functional additive under stirring conditions, controlling the speed at 200 rpm and stirring the reaction for 12 hours, and then centrifugally separating, washing, and drying the obtained product.

[0037] The porogen is polyethylene glycol; the weight average molecular weight of the polyethylene glycol is 200;

[0038] The solvent is 1,2-dichloroethane;

[0039] The metal compounds are zirconium chloride and palladium chloride; the mass ratio of the zirconium chloride to the palladium chloride is 5:1.

[0040] The amine compound is dopamine.

[0041] On the other hand, Example 1 of the present invention provides a method for preparing a porous polymer hydrogen storage material, comprising the following steps:

[0042] (1) A cross-linked porous polymer and a solvent were stirred and mixed at 55° C., and ultrasonically dispersed. The temperature was further raised to 75° C., a porogen was added, and the mixture was reacted to obtain a mixture A;

[0043] (2) The metal compound, the amine compound, and water were stirred and mixed at 55° C., and ultrasonically dispersed for 15 minutes to obtain a mixture B;

[0044] (3) Mixture B is added to mixture A in an inert atmosphere, and the mixture is reacted at 70° C. for 10 h to obtain a porous polymer mixture, which is filtered, washed, and dried under reduced pressure to obtain a porous polymer hydrogen storage material.

[0045] Example 2

[0046] Example 2 of the present invention provides a porous polymer hydrogen storage material. On the one hand, the raw materials for its preparation include, in parts by weight: 100 parts of cross-linked porous polymer, 20 parts of metal compound, 5 parts of amine compound, 3 parts of porogen, 5 parts of solvent and 20 parts of water.

[0047] The raw materials for preparing the cross-linked porous polymer include, by weight, 15 parts of aromatic compound, 1.2 parts of cross-linking agent, 8 parts of functional additive, and 1.2 parts of 1,2-dichloroethane;

[0048] The aromatic compound is a combination of chloromethylated polystyrene and 4,4'-dichloromethyl-1,1'biphenyl; the mass ratio of the chloromethylated polystyrene to 4,4'-dichloromethyl-1,1'biphenyl is 1.2:1.5;

[0049] The chloromethylated polystyrene was purchased from Guangzhou Weber Technology Co., Ltd.; the 4,4'-dichloromethyl-1,1'biphenyl was purchased from J&K Technology Co., Ltd.;

[0050] The cross-linking agent is vinylbenzyl chloride;

[0051] The functional additives include azobisisobutyronitrile, ferric chloride, and tin tetrachloride; the mass ratio of azobisisobutyronitrile, ferric chloride, and tin tetrachloride is 0.5:5:4;

[0052] The preparation method of the cross-linked porous polymer comprises the following steps: adding an aromatic compound and 1,2-dichloroethane to a container and ultrasonically dispersing the mixture for 30 minutes at a temperature of 60° C., raising the temperature to 70° C., adding a cross-linking agent and a functional additive under stirring, controlling the speed to 200 rpm and stirring the mixture for 12 hours, and then centrifugally separating, washing, and drying the mixture.

[0053] The porogen is polyethylene glycol; the weight average molecular weight of the polyethylene glycol is 200;

[0054] The solvent is 1,2-dichloroethane;

[0055] The metal compounds are zirconium chloride and palladium chloride; the mass ratio of the zirconium chloride to the palladium chloride is 6:1.5.

[0056] The amine compound is dopamine.

[0057] Embodiment 2 of the present invention further provides a method for preparing a porous polymer hydrogen storage material, comprising the following steps:

[0058] (1) A cross-linked porous polymer and a solvent were stirred and mixed at 60° C., and ultrasonically dispersed. The temperature was further raised to 80° C., a porogen was added, and the mixture was reacted to obtain a mixture A;

[0059] (2) The metal compound, the amine compound, and water were stirred and mixed at 60° C., and ultrasonically dispersed for 10 minutes to obtain a mixture B;

[0060] (3) Add mixture B to mixture A in an inert atmosphere, react at 80°C for 10 hours to obtain a porous polymer mixture, filter, wash, and then dry under reduced pressure to obtain a porous polymer hydrogen storage material.

[0061] Example 3

[0062] Example 3 of the present invention provides a porous polymer hydrogen storage material. On the one hand, the raw materials for its preparation include, in parts by weight: 80 parts of cross-linked porous polymer, 10 parts of metal compound, 3 parts of amine compound, 1 part of porogen, 3 parts of solvent and 10 parts of water.

[0063] The raw materials for preparing the cross-linked porous polymer include, by weight, 10 parts of aromatic compounds, 0.8 parts of cross-linking agents, 6 parts of functional additives, and 1 part of 1,2-dichloroethane;

[0064] The aromatic compound is a combination of chloromethylated polystyrene and 4,4'-dichloromethyl-1,1'biphenyl; the mass ratio of the chloromethylated polystyrene to 4,4'-dichloromethyl-1,1'biphenyl is 1.2:1.5;

[0065] The chloromethylated polystyrene was purchased from Guangzhou Weber Technology Co., Ltd.; the 4,4'-dichloromethyl-1,1'biphenyl was purchased from J&K Technology Co., Ltd.;

[0066] The cross-linking agent is vinylbenzyl chloride;

[0067] The functional additives include azobisisobutyronitrile, ferric chloride, and tin tetrachloride; the mass ratio of azobisisobutyronitrile, ferric chloride, and tin tetrachloride is 0.5:5:4;

[0068] The preparation method of the cross-linked porous polymer comprises the following steps: adding an aromatic compound and 1,2-dichloroethane to a container and ultrasonically dispersing the mixture for 40 minutes at a temperature of 50° C., raising the temperature to 60° C., adding a cross-linking agent and a functional additive under stirring, controlling the stirring speed at 200 rpm for 12 hours, and then centrifugally separating, washing, and drying the mixture.

[0069] The porogen is polyethylene glycol; the weight average molecular weight of the polyethylene glycol is 200;

[0070] The solvent is 1,2-dichloroethane;

[0071] The metal compounds are zirconium chloride and palladium chloride; the mass ratio of the zirconium chloride to the palladium chloride is 4:0.8.

[0072] The amine compound is dopamine.

[0073] On the other hand, Example 1 of the present invention provides a method for preparing a porous polymer hydrogen storage material, comprising the following steps:

[0074] (1) A cross-linked porous polymer and a solvent were stirred and mixed at 50° C., and ultrasonically dispersed. The temperature was further raised to 70° C., a porogen was added, and the mixture was reacted to obtain a mixture A;

[0075] (2) The metal compound, the amine compound, and water were stirred and mixed at 50° C., and ultrasonically dispersed for 10 minutes to obtain a mixture B;

[0076] (3) Mixture B is added to mixture A in an inert atmosphere, and the mixture is reacted at 60° C. for 12 h to obtain a porous polymer mixture, which is filtered, washed, and dried under reduced pressure to obtain a porous polymer hydrogen storage material.

[0077] Comparative Example 1

[0078] Comparative Example 1 of the present invention provides a porous polymer hydrogen storage material, and its specific implementation is the same as that of Example 1, except that the aromatic compound does not include 4,4'-dichloromethyl-1,1'biphenyl.

[0079] Comparative Example 2

[0080] Comparative Example 2 of the present invention provides a porous polymer hydrogen storage material, and its specific implementation is the same as that of Example 1, except that the cross-linking agent is dichloromethylbenzene.

[0081] Comparative Example 3

[0082] Comparative Example 3 of the present invention provides a porous polymer hydrogen storage material, and its specific implementation is the same as that of Example 1, except that the amine compound is diphenylamine.

[0083] Performance testing methods

[0084] (1) Hydrogen storage performance: The porous polymer hydrogen storage materials prepared in the examples and comparative examples were placed in a volumetric hydrogen storage device to measure the hydrogen storage capacity of the porous polymer hydrogen storage materials at 1 MPa and 77 K. The performance test results are shown in Table 1.

[0085] (2) Specific surface area: The specific surface area of ​​the porous polymer hydrogen storage materials prepared in the examples and comparative examples was measured using a gas adsorption instrument. The test results can be found in Table 1.

[0086] (3) Pore volume ratio: The pore volume ratio of the porous polymer hydrogen storage materials prepared in the examples and comparative examples was measured using a gas adsorption instrument. The test results can be found in Table 1.

[0087] Hydrogen storage capacity (wt%) <![CDATA[Specific surface area (m 2 / g)]]> Pore ​​volume ratio (%) Example 1 6 1486 16.3 Example 2 5.8 1429 15.8 Example 3 5.5 1355 15.5 Comparative Example 1 4.2 1023 10 Comparative Example 2 4.5 1137 12.3 Comparative Example 3 4.8 1259 13.5

Claims

1. A porous polymer hydrogen storage material, characterized in that: The raw materials for preparing the cross-linked porous polymer include at least 80-100 parts by weight, 10-20 parts by weight of a metal compound, 1-5 parts by weight of an amine compound, 1-3 parts by weight of a porogen, 1-5 parts by weight of a solvent, and 10-20 parts by weight of water; the raw materials for preparing the cross-linked porous polymer include at least 10-15 parts by weight of an aromatic compound, 0.5-1.2 parts by weight of a cross-linking agent, 6-8 parts by weight of a functional additive, and 1-1.2 parts by weight of 1,2-dichloroethane; the aromatic compound is chloromethylated polystyrene, 4,4 The invention relates to a combination of chloromethylated polystyrene and 4,4'-dichloromethyl-1,1'biphenyl, wherein the mass ratio of the chloromethylated polystyrene and 4,4'-dichloromethyl-1,1'biphenyl is (0.5-1.2): (0.8-1.5); the cross-linking agent is vinylbenzyl chloride; the porogen is polyethylene glycol, and the weight-average molecular weight of the polyethylene glycol is 200-400; the metal compounds are zirconium chloride and palladium chloride; the mass ratio of the zirconium chloride and palladium chloride is (4-6): (0.8-1.5); and the amine compound is dopamine.

2. The porous polymer hydrogen storage material according to claim 1, characterized in that: The functional auxiliary agent comprises at least two of azobisisobutyronitrile, ferric chloride and tin tetrachloride.

3. A method for preparing a porous polymer hydrogen storage material according to any one of claims 1-2, characterized in that: At least the following steps are included: (1) Mixing the cross-linked porous polymer and the solvent by weight at 50-60°C, and dispersing by ultrasonication, and then heating to 70-80°C, adding the porogen, and reacting to obtain a mixture A; (2) The metal compound, the amine compound, and water are stirred and mixed at 50-60° C., and ultrasonically dispersed for 10-20 minutes to obtain a mixture B; (3) Mixing mixture A and mixture B uniformly, and then ball milling under normal pressure in an inert atmosphere to obtain a mixed powder; (4) Add mixture B to mixture A in an inert atmosphere, react at 60-80°C for 8-12 hours to obtain a porous polymer mixture, filter, wash, and then dry under reduced pressure to obtain a porous polymer hydrogen storage material.