A solid hydrogen storage material and a method for producing the same

Abstract

The application discloses a kind of solid hydrogen storage materials and preparation method thereof.The material is dense solid composite, by hydrogen production agent, non-noble metal boride catalyst and composite lithium cobalt oxide carrier is formed by pressure molding, and water can be supplied hydrogen.Hydrogen production agent is based on sodium borohydride or potassium borohydride;The carrier is modified composite lithium cobalt oxide, and has carrier and catalytic function.This application eliminates liquid solvent and porous support structure, builds synergistic catalytic system, to improve mass and volume hydrogen storage density, and ensure stable hydrogen production rate.Preparation method only involves solid phase mechanical mixing and pressing molding, and process is simple, suitable for large-scale production.The material has the characteristics of portable, safe, and can be used as an ideal hydrogen source, applied to hydrogen fuel cell and other fields.

Description

Technical Field

[0001] This invention belongs to the field of hydrogen energy technology, specifically relating to a solid hydrogen storage material and its preparation method. Background Technology

[0002] Hydrogen energy, as a clean and efficient energy carrier, faces key bottlenecks in realizing a hydrogen economy due to its high-density, lightweight, and portable storage capabilities. Current technologies still have shortcomings in this regard that have not yet been overcome.

[0003] Traditional physical hydrogen storage methods, such as high-pressure gaseous hydrogen storage, face challenges including low volumetric hydrogen storage density and high safety risks; cryogenic liquid hydrogen storage is limited by high liquefaction energy consumption and evaporation losses. Metal hydride hydrogen storage (such as...) Although it is a solid-state hydrogen storage approach, its actual mass hydrogen storage density at the system level is mostly 1.4~2.6 wt%, and the hydrogen storage efficiency needs to be improved; moreover, its hydrogen absorption and desorption kinetics are not good, for example, conventional... Hydrogen release typically requires high temperatures above 300°C and continuous external heating, which can lead to complex hydrogen storage system structures and high energy consumption.

[0004] Chemical hydrides (such as sodium borohydride) are generally known to have a theoretical hydrogen storage density of up to 10.6 wt%, and therefore have received widespread attention in the field of high hydrogen storage materials. Their hydrolysis to produce hydrogen is shown in equation (1):

[0005] (1)

[0006] However, existing technological approaches still have significant limitations in practical applications. Taking the sodium borohydride alkaline aqueous solution approach as an example, US6534033B1 discloses a hydrogen storage system of this type. To ensure... To ensure storage stability and prevent system blockage caused by the precipitation of hydrolysis products, this scheme requires the introduction of a large amount of water (as a reaction medium and anti-precipitant) and a high concentration of stabilizer (such as...). These water and stabilizers, which have no hydrogen storage activity, significantly dilute the actual mass hydrogen storage density of the system, making it far lower than the theoretical hydrogen storage density of sodium borohydride (10.6 wt%), thereby weakening the material's inherent advantage of high hydrogen storage density.

[0007] To address the aforementioned issues, existing solid-state solutions also have shortcomings. WO2007 / 019690A1 discloses a solid-state hydrogen storage solution based on deliquescent materials, utilizing the material's absorption of water vapor from the environment to initiate a hydrolysis reaction. The hydrogen production rate of this solution is highly sensitive to environmental humidity, with performance significantly decreasing in dry environments. Furthermore, the material is prone to deliquescence during the reaction, transforming into a liquid or paste state, leading to volume expansion or changes in material properties, increasing the complexity of system encapsulation and control. In addition, US7306780B1 proposes a structural solution integrating nanocatalysts into sodium borohydride micron-sized particles. While this solution promotes complete reaction, its hydrogen production performance is highly dependent on the uniformity of catalyst distribution within the micron-sized particles, and achieving uniform and controllable distribution of nanocatalysts within micron-sized particles still faces significant process challenges.

[0008] In summary, existing technologies have failed to provide a hydrogen source solution that can simultaneously meet all of the following key performance indicators: 1) achieving high mass hydrogen storage density and volumetric hydrogen storage density at the system level; 2) possessing a dense, portable, and easy-to-operate solid form; 3) having a simple, low-cost, and easily scalable manufacturing process; 4) achieving uniform and stable integration of non-precious metal catalysts; and 5) a stable and controllable hydrogen production process. Summary of the Invention

[0009] This invention provides a solid hydrogen storage material and its preparation method, aiming to achieve higher mass and volume hydrogen storage density. It adopts a stable and portable dense solid form, and its preparation process is simple, low-cost, suitable for industrial production, and can achieve stable, efficient and controllable hydrogen release.

[0010] The solid hydrogen storage material is a solid composite material for hydrogen production. This material is a dense solid obtained by pressure molding of homogeneously mixed powder raw materials. The homogeneously mixed powder raw materials, by mass percentage, comprise:

[0011] (1) 80%~98% of hydrogen-generating agent, wherein the hydrogen-generating agent is selected from one or more of sodium borohydride and potassium borohydride; in a further extended embodiment, the hydrogen-generating agent may also contain ammonia borane, and the extended embodiment may adopt the same preparation method as the core technology solution of this application;

[0012] (2) 2%~20% of catalyst and catalyst support:

[0013] (2.1) The catalyst is a pre-synthesized solid water-insoluble transition metal catalyst, the main active component of which is cobalt boride; in a further extended embodiment, the solid catalyst may also be selected from nickel boride, and the extended embodiment may adopt the same preparation method as the core technology of this application.

[0014] (2.2) The catalyst support is a composite lithium cobalt oxide, which includes lithium cobalt oxide and a modified additive selected from titanium, aluminum, magnesium, silicon metal oxides (or mixtures thereof); the composite lithium cobalt oxide, after modification, has both support and catalytic functions, and forms a synergistic catalytic effect with the catalyst.

[0015] The present invention also provides a method for preparing the above-mentioned solid composite material, comprising the following steps:

[0016] (1) Pre-synthesized catalyst: Solid cobalt boride catalyst powder that is insoluble in water was prepared by chemical reduction method;

[0017] (2) Carrier modification: Lithium cobalt oxide powder is mechanically mixed with the modified material or chemically treated to obtain a modified composite lithium cobalt oxide carrier;

[0018] (3) Homogeneous mixing: The hydrogen production agent, solid catalyst and catalyst support are placed in a mixing device at a predetermined mass ratio for mechanical mixing to obtain a homogeneous powder mixture;

[0019] (4) Press molding: The homogeneous powder mixture is placed in a mold and pressed under a pressure of not less than 10 MPa to form a preset geometric shape;

[0020] (5) Surface stabilization: The solid hydrogen storage material after molding is wrapped with a water-soluble polymer film to form a protective layer.

[0021] Compared with the prior art, the present invention has the following significant advantages:

[0022] 1. Higher Hydrogen Storage Density: This invention employs a dense solid-state molding technology, completely eliminating the large amounts of water and stabilizers found in traditional aqueous solutions, and avoiding the parasitic volume and mass introduced by porous carriers such as sponges and foams. By maximizing the mass fraction of hydrogen-producing active materials, this invention achieves a hydrogen storage density at the system level that far exceeds that of existing technologies in terms of both mass and volume. For example, potassium borohydride has a theoretical volumetric hydrogen storage density of 0.083 g / cm³, and sodium borohydride has 0.112 g / cm³, both exceeding the density of liquid hydrogen at atmospheric pressure (0.07 g / cm³). The dense solid form of this invention retains the inherent high-density advantages of these materials to the maximum extent.

[0023] 2. Simple, low-cost, and scalable manufacturing process and operation method: The core of this invention is "solid-phase mixing-pressure molding," a mature industrial powder metallurgy and tableting process. The method is simple, reliable, low-cost, and easily scaled up for production. In use, simply add the tablets to water for the reaction to occur automatically, requiring no external stirring or additional equipment. The operation is extremely simple and particularly suitable for emergency field scenarios.

[0024] 3. Highly Efficient and Synergistic Catalytic System: This invention employs a pre-synthesized, highly active cobalt boride catalyst, ensuring catalyst uniformity and high activity, thereby improving hydrogen production efficiency. More importantly, this invention uses modified lithium cobalt oxide (composite lithium cobalt oxide) as a catalyst support, which not only provides a stable dispersion platform for the catalyst but also forms a synergistic enhancement effect with the catalyst, further improving the overall catalytic efficiency.

[0025] 4. Strong environmental adaptability: The solid composite material of this invention can work effectively in a wide temperature range of -40℃ to +80℃, and has extremely low requirements for water sources. It can use a variety of water sources, including natural water sources (such as river water, rainwater, and seawater) and non-pure water, and can produce hydrogen without any pretreatment, making it very suitable for applications in special environments such as aerospace, field, emergency, and underwater. Detailed Implementation

[0026] The present invention provides a solid hydrogen storage material, which is a dense solid composite obtained by pressurizing a homogeneous powder mixture. The composite comprises: (1) at least one hydrogen production agent selected from one or more of sodium borohydride and potassium borohydride; (2) at least one solid non-precious metal catalyst selected from cobalt boride; and (3) at least one catalyst support, which is a composite lithium cobalt oxide.

[0027] The solid hydrogen storage material of this invention can spontaneously initiate a hydrolysis reaction simply by adding the tablet to water, without any external stirring or energy input. During the reaction, the tablet maintains continuous contact between the water and the reaction interface through the agitation of bubbles generated by its own gas production and the capillary action of its internal pore structure, ensuring that the reaction proceeds smoothly until it is complete.

[0028] 1. Catalyst Preparation

[0029] The solid catalyst (cobalt boride) can be pre-synthesized by chemical reduction to ensure its high activity and uniformity, and to avoid consuming the hydrogen-producing agent in the subsequent hydrogen production process.

[0030] Taking cobalt borides as an example, their preparation method includes: preparing cobalt salts (such as cobalt chloride hexahydrate, ... The cobalt salt solution is dissolved in deionized water, and an aqueous solution of the complexed hydride (such as sodium borohydride) is added dropwise to the solution under stirring. A black precipitate is immediately formed. After continuous stirring, the precipitate is collected by centrifugation or filtration, repeatedly washed with deionized water and anhydrous ethanol to remove impurity ions, and finally dried in a vacuum drying oven at 60°C to obtain a highly active amorphous cobalt boride catalyst powder (with an average particle size controllable in the range of 30~50 nm) stored in an oxygen-free environment.

[0031] Similarly, nickel borides can be produced by nickel salts (such as nickel chloride hexahydrate, ... It is prepared by chemical reduction.

[0032] 2. Preparation of catalyst support

[0033] The catalyst support is a composite lithium cobalt oxide. This support contains lithium cobalt oxide (…). It contains at least one metal oxide selected from titanium, aluminum, magnesium, and silicon as a modifying additive.

[0034] The preparation method of this composite lithium cobalt oxide support includes: mixing battery-grade lithium cobalt oxide powder with one or more modifying additives (such as... , , , Powders of (etc.) are processed by mechanical mixing (such as in a ball mill or mixer) to obtain modified composite lithium cobalt oxide carrier powder.

[0035] The content of the modified additive, based on the total mass of the carrier, shall not exceed 40%. This carrier primarily provides a high specific surface area and suitable pore structure to effectively disperse the nanocatalyst and prevent its aggregation and deactivation during the reaction; simultaneously, the modified additive (such as...) , (etc.) can adjust the hydrophilicity or hydrophobicity of the carrier surface, promote the diffusion of water molecules, and thus form a synergistic effect with the catalyst.

[0036] 3. Preparation of solid hydrogen storage materials

[0037] Preferably, the method of the present invention further includes performing a mechanochemical treatment on the powder before pressing and molding. The mechanochemical activation treatment refers to a physicochemical process that uses mechanical force (such as ball milling, vibratory milling, etc.) to perform high-energy grinding of the powder to destroy the oxide film on the particle surface, increase active sites, and improve solid-solid interface contact. Typical high-energy ball milling conditions include: rotation speed 200-800 rpm, processing time 0.5-10 hours, and ball-to-material ratio 10:1 to 50:1. Specific parameters can be adjusted according to the equipment type and material characteristics. This process can be carried out under an inert atmosphere using a ball mill, vibratory mill, or high-energy mixer.

[0038] The preparation method of the solid hydrogen storage material of the present invention includes the following steps:

[0039] (1) Mixing: The hydrogen-producing agent (one or more of sodium borohydride and potassium borohydride) that has been pre-crushed (e.g., ground to a particle size of less than 50 µm), the cobalt boride catalyst obtained in step 1, and the composite lithium cobalt oxide catalyst support obtained in step 2 are placed in a mixing device (e.g., a V-type mixer or a three-dimensional motion mixer) according to a predetermined mass ratio (e.g., the hydrogen-producing agent accounts for 80% to 98%, and the total of the catalyst and support accounts for 2% to 20%) and mechanically mixed under the protection of an inert gas to obtain a homogeneous powder mixture.

[0040] (2) Compression molding: The homogeneous powder mixture is placed in a mold of a specific shape (such as a cylindrical mold), and uniaxial cold pressing (preferably about 50 MPa) is performed using a hydraulic press or punch at a pressure of not less than 10 MPa (about 100 kg / cm²). Then, the mold is demolded to obtain a solid hydrogen source tablet with sufficient mechanical strength and high density.

[0041] (3) Packaging: The molded solid hydrogen storage material is packaged into water-soluble packaging (such as water-soluble polymer film). This protective layer can prevent the material from reacting prematurely with moisture in the air during storage and transportation, and it dissolves quickly when it comes into contact with water.

[0042] In the following examples, the hydrogen production rate and theoretical value are calculated based on the following standards:

[0043] 1. Theoretical hydrogen production capacity of hydrogen-producing agents: Sodium borohydride and potassium borohydride are calculated based on the complete hydrolysis producing 4 equivalents of hydrogen gas (assuming...). For example); the ammonia borane involved in Example 5 is catalytically hydrolyzed at room temperature and pressure to produce 3 equivalents of hydrogen gas ( )calculate.

[0044] 2. General calculation of hydrogen production rate: The ratio of the measured gas volume (corrected for water vapor partial pressure and system dead volume) to the theoretical hydrogen production volume at 25℃ and 101.3 kPa. The theoretical hydrogen production volume is calculated based on the ideal gas law, with a gas molar volume of 24.47 L / mol at 25℃.

[0045] Example 1: Modified carrier

[0046] (1) Preparation of catalyst support: Weigh 76 parts by mass of battery-grade catalyst support. Powder and 24 parts by weight The powder was prepared into modified carrier A by mechanical mixing.

[0047] (2) Catalyst preparation: Cobalt borate was prepared by reducing cobalt chloride hexahydrate with sodium borohydride aqueous solution according to the method described in the instructions. Catalyst powder B.

[0048] (3) Solid material preparation and molding: Weigh 2 grams of sodium borohydride ( 0.1 g of catalyst powder B and 0.1 g of modified support A (i.e., the total mass of catalyst and support is about 9.1%) are thoroughly mechanically mixed.

[0049] (4) Compression molding: The above mixed powder is placed in a mold and compressed into a round disc (tablet) with a diameter of 13 mm under a pressure of about 50 MPa (500 kg / cm²).

[0050] (5) Performance test: Place the tablet (total weight 2.2 g) in a 250 mL three-necked flask, connect the gas delivery tube to the gas flow meter or water collection device, add 10 mL of deionized water at room temperature (about 25 °C) and normal pressure, let the flask stand without any stirring, and immediately seal the mouth of the flask. The generated hydrogen gas is collected and measured through the gas delivery tube.

[0051] (6) Results: The reaction started rapidly. The tablet maintained the reaction in water by relying on the micro-disturbance generated by its own gas production and the porous structure, and released hydrogen steadily. The cumulative hydrogen production reached 4920 mL (measured at room temperature 25℃ and normal pressure, and corrected), the hydrogen production rate was about 95.0% of the theoretical value (theoretical value 5180 mL), and the average hydrogen production rate was about 410 mL / min. The reaction was completed within 12 minutes, the tablet completely disintegrated, and only dispersed catalyst and carrier powder precipitated at the bottom of the flask, without any unreacted material agglomerating into hard lumps.

[0052] Example 2: Multi-component modified carrier ( )

[0053] (1) Carrier preparation: Weigh 64 parts by weight of battery grade Powder, 24 parts by weight and 12 parts by weight Modified carrier C was prepared by mechanical mixing.

[0054] (2) Testing: The remaining steps are the same as in Example 1, except that modified carrier A is replaced with modified carrier C.

[0055] (3) Results: The hydrogen production performance was comparable to that of Example 1. The reaction was stable and required no external stirring. The cumulative hydrogen production reached 4890 mL (measured at room temperature 25℃ and normal pressure, and corrected). The hydrogen production rate was approximately 94.4% of the theoretical value (theoretical value 5180 mL), indicating that... The introduction of [the substance] did not reduce catalytic activity and may have improved the structural stability of the support in an alkaline environment.

[0056] Example 3: Modified carrier

[0057] (1) Carrier preparation: Weigh 75 parts by weight of battery grade Powder and 25 parts by weight Modified carrier D was prepared by mechanical mixing.

[0058] (2) Testing: The remaining steps are the same as in Example 1, except that modified carrier A is replaced with modified carrier D.

[0059] (3) Results: The reaction was stable and required no external stirring. The cumulative hydrogen production reached 4865 mL (measured at room temperature 25℃ and normal pressure, and corrected), and the hydrogen production rate was approximately 93.9% of the theoretical value (theoretical value 5180 mL), proving that... It is also suitable as a modifying additive.

[0060] Example 4: Different hydrogen production agents ( )

[0061] (1) Formula adjustment: 2.0 g of the formula in Example 1 was adjusted. Replace with 2.0 g potassium borohydride ( ).

[0062] (2) Result: Due to The molar mass (53.94 g / mol) is greater than The hydrogen yield per unit mass is relatively low. The theoretical hydrogen yield is approximately 3630 mL (at ambient pressure and 25°C). The measured hydrogen yield is approximately 3350 mL (measured at ambient pressure and 25°C, corrected), with a hydrogen yield rate of approximately 92.3% of the theoretical value and a reaction time of approximately 16 minutes. No external stirring is required during the reaction, demonstrating the universality of the formulation of this invention for different alkali metal borohydrides.

[0063] Example 5: Mixed hydrogen production agents ( )

[0064] (1) Formula adjustment: Use 1.0 g sodium borohydride ( ) and 1.0 g ammoniaborane ( A mixture of sodium borohydride and ammonia borane is used as a hydrogen-producing agent. Based on the ambient temperature and pressure catalytic hydrolysis system of this invention, the theoretical hydrogen production of sodium borohydride, calculated based on complete hydrolysis, is approximately 2590 mL; the theoretical hydrogen production of ammonia borane is approximately 2380 mL. Combined, the theoretical total hydrogen production of the mixed system is approximately 4970 mL.

[0065] (2) Results: The reaction rate was slightly slower in the initial stage (due to the high activation energy of ammonia borane hydrolysis), but the reaction lasted longer. The total hydrogen production was approximately 4650 mL (measured at room temperature 25℃ and normal pressure, and corrected), and the hydrogen production rate was approximately 93.5% of the theoretical value. No external stirring was required during the reaction, which verifies the feasibility of this invention supporting multi-component hydrogen production agents.

[0066] Example 6: Mechanochemical activation enhancement

[0067] (1) Process adjustment: After the mixing step in Example 1, an additional "mechanical and chemical activation treatment" step is added: the mixed powder is placed in a ball mill under inert gas protection for high-energy ball milling treatment, and then compressed into tablets.

[0068] (2) Results: The reaction induction period of the activated sample almost disappeared, and the reaction rate was significantly improved. The reaction was completed in about 5 minutes, with a cumulative hydrogen production of about 4980 mL (measured at room temperature 25℃ and normal pressure, and corrected), and the hydrogen production rate was about 96.1% of the theoretical value. No external stirring was required during the reaction. This indicates that the mechanochemical activation energy significantly improves the solid-solid interface and greatly enhances the reaction kinetics.

[0069] Example 7: Broad-spectrum water source adaptability test

[0070] The tablets prepared in Example 1 were tested at room temperature (approximately 25°C) and atmospheric pressure using different water sources (10 mL for each test). No stirring was performed during any of the tests.

[0071] (1) Rainwater: The reaction proceeded smoothly, with a hydrogen production of approximately 4680 mL (measured at room temperature 25℃ and normal pressure, and corrected), and a hydrogen production rate of approximately 90.3% of the theoretical value (theoretical value 5180 mL). A slight increase in the reaction rate was observed in the initial stage of the reaction.

[0072] (2) Tap water: The reaction was stable, and the hydrogen production was about 4800 mL (measured at room temperature 25℃ and normal pressure, and corrected). The hydrogen production rate was about 92.7% of the theoretical value (theoretical value 5180 mL). The trace residual chlorine in tap water had no obvious toxic effect on the catalyst activity.

[0073] (3) Simulated seawater (3.5%) In solution: the reaction proceeded normally, with a hydrogen production of approximately 4640 mL (measured at room temperature, 25°C, and normal pressure, and corrected), and a hydrogen production rate of approximately 89.6% of the theoretical value (theoretical value 5180 mL). The high concentration of chloride ions did not cause catalyst poisoning, demonstrating excellent salt tolerance.

[0074] Conclusion: Example 7 demonstrates that the solid hydrogen storage material of the present invention has a strong tolerance to water quality and can utilize widely available water sources in nature without pretreatment, making it very suitable for field and emergency scenarios.

[0075] Comparative Example 1 (Carrier Unmodified)

[0076] Use pure (Unmodified) as a carrier, other conditions are the same as in Example 1.

[0077] Results: The reaction started slowly and the rate decreased significantly in the middle and later stages. The total hydrogen production was approximately 62% of the theoretical value, or about 3210 mL (measured at room temperature, 25°C, and atmospheric pressure, and corrected), significantly lower than the near-theoretical hydrogen production in Example 1. This indicates that the unmodified reaction... The carrier exhibits poor dispersibility and synergistic catalytic effect.

[0078] Comparative Example 2 (simple physical mixing, without pressure)

[0079] The mixed powder with the same proportions as in Example 1 was not subjected to any tableting process and was directly and loosely packed into a 250mL three-necked flask. 10 mL of deionized water was added without stirring.

[0080] Results: The powder rapidly agglomerated upon contact with water. Observation revealed that after approximately 3 minutes of reaction, a dense, white, hard mass formed at the bottom of the flask, encapsulating the unreacted powder agglomerates, and bubble production decreased sharply. After the reaction, analysis upon crushing revealed that the hard mass still contained a large amount of unreacted sodium borohydride, resulting in a hydrogen conversion rate of less than 48%, with a measured hydrogen production of approximately 2480 mL (measured at room temperature (25°C) and normal pressure, corrected). In contrast, the tablets formed by pressure molding in Example 1 maintained an intact framework throughout the reaction. The framework disintegrated in the later stages of the reaction, and after the reaction, only dispersed catalyst and carrier powder precipitated at the bottom of the flask. No hard masses formed by unreacted substances were observed, indicating a complete reaction and hydrogen production close to the theoretical value. This demonstrates that the dense pressure molding technology of this invention, by forming a structurally stable solid composite, effectively avoids reaction obstruction caused by powder agglomeration and product encapsulation, ensuring the complete hydrolysis reaction. List of background technical documents

[0081] 1.Millennium Cell, Inc. SYSTEM FOR HYDROGEN GENERATION: US6534033B1[P]. 2003-03-18.

[0082] 2.HERA, Hydrogen Storage Systems Inc. HYDROGEN GENERATION THROUGHREACTIONS INVOLVING SORPTION MECHANISMS: WO2007 / 019690A1[P]. 2007-02-22.

[0083] 3. Sandia Corporation. METHOD OF GENERATING HYDROGEN GAS FROM SODIUMBOROHYDRIDE: US7306780B1[P]. 2007-12-11.

Claims

1. A solid hydrogen-producing composition, characterized in that, The catalyst comprises: a hydrogen-producing agent selected from one or more of sodium borohydride and potassium borohydride; a solid catalyst selected from cobalt boride; and a catalyst support, which is a modified composite lithium cobalt oxide, wherein the modified composite lithium cobalt oxide comprises lithium cobalt oxide and at least one metal oxide modifier selected from titanium dioxide, aluminum oxide, magnesium oxide, and silicon dioxide; wherein the solid catalyst is mixed with the catalyst support and dispersed in the hydrogen-producing agent.

2. The solid hydrogen-producing composition according to claim 1, characterized in that, The total mass of the catalyst and catalyst support accounts for 2% to 20% of the total mass of the solid hydrogen production composition.

3. A method for preparing the solid hydrogen-producing composition according to claim 1 or 2, characterized in that, The process includes the following steps: mechanically mixing a hydrogen-producing agent, a solid catalyst, and a catalyst support to obtain a homogeneous powder mixture; pressing the homogeneous powder mixture into a mold; and dispensing the molded solid hydrogen-producing composition into water-soluble packaging.

4. The method according to claim 3, characterized in that, The hydrogen-producing agent is selected from one or more of sodium borohydride and potassium borohydride; the solid catalyst is selected from cobalt boride; the catalyst support is a modified composite lithium cobalt oxide, which includes lithium cobalt oxide and at least one metal oxide modifier selected from titanium dioxide, aluminum oxide, magnesium oxide, and silicon dioxide.

5. The method according to claim 3, characterized in that, The cobalt boride is prepared by reducing cobalt salt.

6. The method according to claim 3, characterized in that, Before compression molding, the hydrogen-generating agent, solid catalyst, and catalyst support are subjected to mechanochemical treatment.

7. The method according to claim 3, characterized in that, The compression molding is carried out under a pressure of not less than 10 MPa.

8. A method for producing hydrogen, characterized in that, Water or an aqueous liquid is added to the solid hydrogen-producing composition of claim 1 or 2 to produce hydrogen at an ambient temperature of -40°C to +80°C.

9. The method according to claim 8, characterized in that, The water is either from a natural source or is untreated.