High-temperature solid hydrogen storage device started without external heat source and operation method of high-temperature solid hydrogen storage device

Abstract

The invention discloses a high-temperature solid hydrogen storage device started without an external heat source. The high-temperature solid hydrogen storage device consists of a hydrogen storage unit 1, an initiation structure 2, a gas supply system 3, a shell 4 and a temperature control device 5, the hydrogen storage unit is composed of a solid hydrogen storage material bed trigger area and a solid hydrogen storage material bed sweep area; the initiating structure consists of a solid hydrogen storage initiating material, a bed layer bracket and a fixed rod; the gas supply system consists of a gas inlet / outlet, a filter screen, a clearance space and a communicating pore; the shell is composed of a hydrogen storage tank barrel, a hydrogen storage tank end cover and a sealing gasket. The temperature control device exchanges heat through heat exchange fluid. The invention discloses an operation method of a high-temperature solid hydrogen storage device started without an external heat source. The operation method comprises the following steps: 1, preparation before hydrogen absorption; 2, starting a hydrogen absorption process; and 3, controlling the hydrogen absorption process.

Description

Technical Field

[0001] The present invention belongs to the field of hydrogen energy storage and transportation, and particularly relates to a high-temperature solid-state hydrogen storage device that can be started without an external heat source and an operating method thereof. Background Art

[0002] When solid-state hydrogen storage materials are used in the laboratory, only a small amount of solid-state hydrogen storage material is used, and the temperature of the solid-state hydrogen storage material bed is simple and fast. However, in actual application, due to the large mass and low thermal conductivity of the solid-state hydrogen storage material, conventional high-temperature solid-state hydrogen storage devices have the problem of difficulty and long time to heat the solid-state hydrogen storage material bed. The reason is that currently existing solid-state hydrogen storage devices use the traditional heat exchange fluid startup method, that is, the entire medium- and high-temperature solid-state hydrogen storage material bed is heated to a high temperature by a heat exchange fluid, and then hydrogen is introduced to carry out the hydrogen absorption reaction. For example, existing document 1 (Large scale magnesium hydride tank coupled with an external heat source, International Journal of Hydrogen Energy, 2012, 37:9103-9111) uses high-temperature heat transfer oil to heat the MgH2 bed to approximately 240°C before performing the hydrogen absorption operation. During the subsequent hydrogen absorption reaction, the heat transfer oil temperature is also maintained at approximately 240°C to remove the large amount of heat generated by the hydrogen absorption reaction. However, this type of heat exchange fluid-based startup method has the following two technical problems:

[0003] 1. Due to the use of heat exchange fluid, the required heat exchange fluid has the basic characteristics of large specific heat capacity and large volume. Therefore, during the heating process, there are problems such as high energy consumption and long heating time, which is referred to as the energy consumption-time problem. Specifically, in existing literature 1, the start-up time of the hydrogen absorption reaction of the solid hydrogen storage material bed is 2 hours;

[0004] 2. Due to the use of heat exchange fluid, there is a thermal management system that needs to realize the heating and cooling functions at the same time. Therefore, after the startup process is completed, the heat exchange fluid is in a high temperature state. At the same time, due to the large specific heat capacity of the heat exchange fluid, the temperature of the heat exchange fluid drops slowly, which directly leads to the low heat exchange efficiency of the heat exchange fluid in the subsequent hydrogen absorption reaction process, and ultimately leads to the problem of low cooling efficiency. The reaction temperature cannot be controlled in time, which is referred to as the temperature control problem.

[0005] To address the energy-time issue mentioned above, a thermal management system can employ electric heating. For example, existing literature 2 (Experimental and numerical study of a magnesium hydride tank, International Journal of Hydrogen Energy, 2010, 35:6311-6322) uses heating coils wrapped around the outer wall of a hydrogen storage tank filled with MgH2 material. The coils heat the material bed to 300°C before performing the hydrogen absorption operation.

[0006] However, the problem with this technical solution consists of two aspects:

[0007] 1. The electric heating coil is set outside the hydrogen storage device, which directly leads to a long heating distance from the electric heating coil to the center of the solid hydrogen storage material bed. In addition, an additional insulation device needs to be set outside the heating coil;

[0008] 2. The electric heating coil needs to heat the entire medium- and high-temperature solid hydrogen storage material bed. The energy consumption required for heating increases in direct proportion to the mass of the heated solid hydrogen storage material.

[0009] The combined consequence of the above two problems is that the startup time and energy consumption cannot be effectively reduced. Specifically, the startup time of the existing document 2 still takes more than 1 hour.

[0010] In addition, the existing document 2 still cannot effectively solve the problem 2, temperature control problem, in the existing document 1. The reason is that the existing document 2 uses an electric heating coil as the heating system, that is, there is no need to use a heat exchange fluid, but instead uses a technical solution of setting cooling air inside the hydrogen storage device for cooling. However, since the cooling air is set inside the hydrogen storage device, there is a problem of small heat exchange area, which directly leads to the inability to quickly remove the heat generated by the hydrogen absorption reaction, that is, the heat exchange effect is poor; at the same time, since the heating coil of the existing document 2 is arranged on the outer wall of the hydrogen storage device, it directly leads to the obstruction of the contact between the hydrogen storage device and the external low-temperature environment, that is, there is a problem of large heat dissipation resistance of the hydrogen storage device to the external low-temperature environment.

[0011] Furthermore, based on the above analysis of the prior art, it is clear that even if the aforementioned issues 1, energy consumption and time, and 2, temperature control, are resolved, the underlying principle of the technical solution is to trigger the hydrogen storage reaction through external energy supply, i.e., the essential technical feature includes an additional energy supply device. This technical feature directly increases the structural complexity of the hydrogen storage device. Summary of the Invention

[0012] The purpose of the present invention is to provide a high-temperature solid-state hydrogen storage device that can be started without an external heat source, and an operating method thereof. To address the technical issues of the prior art that require additional energy supply devices, a completely different initiation principle can be employed. Therefore, in order to achieve a high-temperature solid-state hydrogen storage device that can be started without an external heat source, the inventive principle of the present invention is as follows:

[0013] 1. A solid-state hydrogen storage initiation material is used to form an initiation structure to activate the solid-state hydrogen storage functional material. The two types of solid-state hydrogen storage materials absorb hydrogen and release heat in a cascade within the hydrogen storage device, achieving a technical effect of eliminating the need for external energy supply, thereby reducing the need for external energy supply devices, and ultimately achieving the technical effect of simplifying the system structure and reducing the system volume;

[0014] 2. Based on the technical principle of no external heat source, the heat exchange fluid does not need to be actively heated, but only needs to remove the heat of the hydrogen absorption reaction of the solid hydrogen storage material. Therefore, it has the characteristics of low heat exchange fluid temperature, that is, it has the characteristics of large heat exchange temperature difference between the solid hydrogen storage material bed and the solid hydrogen storage material bed, which directly leads to the technical effect of fast heat transfer rate;

[0015] 3. By placing the initiating structure inside the hydrogen storage device, the heat transfer distance from the initiating structure to the solid hydrogen storage material bed can be shortened. At the same time, the heat dissipation to the external environment during the startup process can be reduced on the basis of reducing the insulation structure;

[0016] 4. A method of heating part of the solid-state hydrogen storage material to trigger the reaction of the remaining hydrogen storage material is adopted, thereby reducing the energy consumption required to start the hydrogen absorption reaction and reducing the amount of solid-state hydrogen storage initiating material used. The principle is that, first, the solid-state hydrogen storage initiating material reacts with hydrogen at room temperature and releases heat, thereby raising the temperature of the solid-state hydrogen storage initiating material to the temperature required for the reaction of the solid-state hydrogen storage functional material; then, the solid-state hydrogen storage initiating material heats part of the solid-state hydrogen storage functional material near the bed support to start the hydrogen absorption reaction of this part of the solid-state hydrogen storage functional material; then, the reaction of the solid-state hydrogen storage initiating material is completed, and the remaining solid-state hydrogen storage functional material can trigger subsequent reactions through the heat released by the hydrogen absorption reaction of the reacted part of the solid-state hydrogen storage material, until the hydrogen absorption of the entire solid-state hydrogen storage functional material bed is completed.

[0017] In order to achieve the above object, the present invention adopts the following technical solutions:

[0018] A high-temperature solid-state hydrogen storage device that is activated without an external heat source, comprising a hydrogen storage unit, an initiation structure, a gas supply system, a housing, and a temperature control device;

[0019] The hydrogen storage unit consists of a solid hydrogen storage material bed triggering area and a solid hydrogen storage material bed swept area;

[0020] In the hydrogen storage unit, the solid-state hydrogen storage material bed triggering zone and the solid-state hydrogen storage material affected zone are both composed of solid-state hydrogen storage functional material particles and pores; the solid-state hydrogen storage functional material is a large-capacity solid-state hydrogen storage material;

[0021] One side of the solid hydrogen storage material bed triggering zone is connected to the bed support in the triggering structure, and the other side is connected to the solid hydrogen storage material bed affected area; the distance from the solid hydrogen storage material bed triggering zone to the bed support is 0-15mm;

[0022] A gap space is left between the hydrogen storage unit and the side wall of the hydrogen storage tank cylinder in the shell and the upper and lower walls of the hydrogen storage tank.

[0023] The initiation structure consists of solid hydrogen storage initiation material, bed support and fixing rod;

[0024] In the initiation structure, the solid-state hydrogen storage initiation material is a low-temperature solid-state hydrogen storage material;

[0025] The bed support is composed of a partition plate and a sleeve;

[0026] The partition plate is fixed at the bottom of the sleeve, and the upper side of the partition plate contacts the triggering area of ​​the solid hydrogen storage material bed;

[0027] The outer surface of the sleeve contacts the hydrogen storage unit, and the inner surface of the sleeve matches the fixing rod;

[0028] At least one of the partition plates of the fixed rod and the bed support is a hollow structure for loading a solid hydrogen storage initiating material; when the fixed rod or the bed support is loaded with the solid hydrogen storage initiating material, the fixed rod or the bed support is provided with a connecting pore for hydrogen to enter the fixed rod or the bed support and react with the solid hydrogen storage initiating material; the mass of the solid hydrogen storage initiating material bed does not exceed 1 / 2 of the mass of the solid hydrogen storage functional material in the hydrogen storage unit;

[0029] Multiple bed supports are fixed in series on the fixed rod, with gaps between the bed supports;

[0030] The gas supply system consists of gas inlets and outlets, filters, interstitial spaces and connecting pores;

[0031] In the gas supply system, a filter is provided at the lower side of the gas inlet and outlet to filter the gas entering and leaving the hydrogen storage tank;

[0032] The outer shell is composed of a hydrogen storage tank cylinder, a hydrogen storage tank end cover and a sealing gasket;

[0033] In the shell, the inner cavity of the hydrogen storage tank cylinder accommodates the hydrogen storage unit, the triggering structure and the gas supply system; the upper edge of the hydrogen storage tank cylinder is provided with a cylinder flange connection hole; and the bottom of the hydrogen storage tank cylinder is fixed with a fixing rod;

[0034] The edge of the hydrogen storage tank end cover is provided with an end cover flange connection hole; the end cover of the hydrogen storage tank is provided with a gas inlet and outlet;

[0035] The cylinder flange connection hole and the end cover flange connection hole are connected by bolts; when the hydrogen storage tank cylinder and the hydrogen storage tank end cover are connected, a sealing gasket is provided between the hydrogen storage tank cylinder and the hydrogen storage tank end cover.

[0036] The temperature control device uses heat exchange fluid to exchange heat;

[0037] In the temperature control device, the temperature control device is arranged outside the hydrogen storage tank cylinder and is used to take away the heat generated by the hydrogen absorption reaction of the solid hydrogen storage material.

[0038] A method for operating a high-temperature solid-state hydrogen storage tank without external heat source startup comprises the following steps:

[0039] Step 1, preparation before hydrogen absorption, first, fill the hydrogen storage unit in the hydrogen storage tank, fill the solid hydrogen storage initiation material in the initiation structure, then seal the hydrogen storage tank, perform vacuum operation to remove impurity gas in the hydrogen storage tank, and finally, start the temperature control device to achieve temperature control of the hydrogen storage tank;

[0040] Step 2, starting the hydrogen absorption process, first, hydrogen is introduced into the hydrogen storage tank through the gas supply system to make the hydrogen pressure reach the operating pressure; the hydrogen first reacts with the solid-state hydrogen storage initiating material to generate heat, thereby increasing the temperature of the solid-state hydrogen storage initiating material; then, the heat generated by the hydrogen absorption reaction of the solid-state hydrogen storage initiating material is transferred to the hydrogen storage unit, heating the triggering zone of the solid-state hydrogen storage material bed; finally, the reaction in the triggering zone of the solid-state hydrogen storage material bed releases a large amount of heat, driving the continuous reaction in the affected zone of the solid-state hydrogen storage material bed;

[0041] Step 3, control of the hydrogen absorption process, by adjusting the speed of the heat exchange fluid in the temperature control device to control the progress of the hydrogen absorption reaction in the trigger area of ​​the solid hydrogen storage material bed and the affected area of ​​the solid hydrogen storage material; after the hydrogen absorption reaction is completed or the control is completed, the gas supply system stops supplying gas, and at the same time, the temperature control device lowers the temperature of the hydrogen storage tank to room temperature.

[0042] When the solid-state hydrogen storage functional material is Mg2Ni and the solid-state hydrogen storage initiating material is LaNi5,

[0043] In step 1, the hydrogen storage unit is cylindrical, with a diameter of 15 cm, a height of 5 cm, and a porosity of 0.3;

[0044] In the initiation structure, the solid hydrogen storage initiation material is placed in a cylindrical partition plate; the partition plate has a diameter of 14 cm and a height of 0.5 cm, and the porosity of the solid hydrogen storage initiation material bed is 0.63;

[0045] The temperature control device uses heat exchange fluid, the heat exchange fluid is thermal oil, and the heat transfer coefficient is 200-5000W / m 2, the heat transfer fluid temperature is 288.15-308.15K;

[0046] In step 2, the operating pressure in the hydrogen storage tank is 1-5 MPa.

[0047] After experimental testing, the technical effects of the present invention were compared with the traditional heat exchange fluid startup method. It was found that the startup time of the hydrogen storage device of the present invention is only 5.3% of the traditional method, no external energy is required, and the completion time of the hydrogen absorption reaction of the hydrogen storage device is shortened by 55.4%.

[0048] Compared with the prior art, the present invention has the following beneficial effects:

[0049] 1. The present invention provides a high-temperature solid-state hydrogen storage device that can be started without an external heat source, and an operating method thereof. By combining the operating temperature ranges of a solid-state hydrogen storage initiating material with a lower starting temperature and a solid-state hydrogen storage functional material with a higher starting temperature, the hydrogen absorption reaction of the solid-state hydrogen storage initiating material and the solid-state hydrogen storage functional material is triggered in a cascade manner without external energy supply, thereby reducing the dependence of the hydrogen storage device's hydrogen absorption reaction on external energy supply.

[0050] 2. Placing the initiation structure inside the hydrogen storage device shortens the distance between the initiation structure and the bed of solid hydrogen storage functional materials, thereby increasing the heat transfer rate. Furthermore, only part of the solid hydrogen storage functional materials is heated, thereby increasing the startup speed of the hydrogen storage device.

[0051] 3. Placing the initiating structure inside the hydrogen storage device reduces heat loss to the surrounding low-temperature environment. Moreover, heating only a portion of the solid-state hydrogen storage functional material can trigger the solid-state hydrogen storage functional material bed to continuously absorb hydrogen, thereby reducing the energy consumption required to start the hydrogen absorption reaction and minimizing the impact of the solid-state hydrogen storage initiating material with low hydrogen storage capacity on the capacity of the hydrogen storage device.

[0052] 4. The heat transfer performance between the temperature control system outside the hydrogen storage device and the solid hydrogen storage material bed is improved. Compared with the traditional heat exchange fluid startup method, the initial fluid temperature is low, the heat transfer temperature difference is large, the temperature control device cools down quickly, the heat load is small, and the hydrogen storage device's hydrogen absorption reaction is completed in a short time;

[0053] 5. The triggering structure and temperature control device in the thermal management system of the hydrogen storage device do not affect each other. The thermal management system structure and internal heat flow are simple and clear, and the operation and control methods are simple. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] Figure 1This is a structural schematic diagram of a high-temperature solid-state hydrogen storage device that is not started by an external heat source in Example 1, wherein 1 is a hydrogen storage unit, 1-1 is a triggering area of ​​a solid hydrogen storage material bed, 1-2 is a spread area of ​​a solid hydrogen storage material bed, 2 is a triggering structure, 2-1 is a bed support, 2-2 is a fixing rod, 3 is a gas supply system, 3-1 is a gas inlet and outlet, 3-2 is a filter, 4 is an outer shell, 4-1 is a hydrogen storage tank cylinder, 4-1-1 is a cylinder flange connection hole, 4-2 is a hydrogen storage tank end cover, 4-2-1 is an end cover flange connection hole, 4-3 is a sealing gasket, and 5 is a temperature control device;

[0055] Figure 2 This is a schematic diagram of the bed support structure of Example 1, wherein 2-1-1 is a sleeve and 2-1-2 is a partition plate;

[0056] Figure 3 This is a graph showing the change in bed reaction fraction over time during the startup process of Example 1;

[0057] Figure 4 This is a structural schematic diagram of a high-temperature solid-state hydrogen storage device that is activated without an external heat source and in which the function of the triggering structure is realized by a fixed rod in Example 2. DETAILED DESCRIPTION

[0058] The present invention is further described in detail through embodiments and in conjunction with the accompanying drawings, but the present invention is not limited thereto.

[0059] Example 1

[0060] A high-temperature solid-state hydrogen storage device that is activated without an external heat source, such as Figure 1 As shown, it consists of a hydrogen storage unit 1, an initiating structure 2, a gas supply system 3, a shell 4 and a temperature control device 5.

[0061] The specific position and structure relationship of the hydrogen storage unit 1 is as follows: Figure 1 As shown, it consists of a solid hydrogen storage material bed triggering area 1-1 and a solid hydrogen storage material bed sweeping area 1-2.

[0062] The solid-state hydrogen storage material bed triggering zone 1-1 and the solid-state hydrogen storage material affected zone 1-2 are both composed of solid-state hydrogen storage functional material particles and pores; the solid-state hydrogen storage functional material is a large-capacity solid-state hydrogen storage material;

[0063] One side of the solid hydrogen storage material bed triggering zone 1-1 is connected to the bed support 2-1 in the triggering structure 2, and the other side is connected to the solid hydrogen storage material bed affected zone 1-2; the distance between the solid hydrogen storage material bed triggering zone 1-1 and the bed support 2-1 is 0-15mm;

[0064] A gap is left between the hydrogen storage unit 1 and the side walls of the hydrogen storage tank cylinder 4 - 1 in the housing 4 and the upper and lower walls of the hydrogen storage tank.

[0065] The specific positional structural relationship of the initiating structure 2 is as follows Figure 1 As shown, it is composed of solid hydrogen storage initiation material, bed support 2-1 and fixing rod 2-2; it is used to provide heat for the start-up of the hydrogen storage tank and support the hydrogen storage unit;

[0066] The solid-state hydrogen storage initiating material is a low-temperature solid-state hydrogen storage material;

[0067] The specific position and structural relationship of the bed support 2-1 is as follows Figure 2 As shown, it is composed of a partition plate 2-1-1 and a sleeve 2-1-2;

[0068] The partition plate 2-1-1 is fixed at the bottom of the sleeve 2-1-2, and the upper side of the partition plate 2-1-1 is in contact with the solid hydrogen storage material bed triggering area 1-1;

[0069] The partition plate 2-1-1 is a hollow structure for loading the solid hydrogen storage initiating material; the partition plate 2-1-1 is provided with a connecting pore for hydrogen to enter the partition plate 2-1-1 and react with the solid hydrogen storage initiating material; the mass of the solid hydrogen storage initiating material shall not exceed 1 / 2 of the mass of the solid hydrogen storage functional material in the hydrogen storage unit 1;

[0070] The outer surface of the sleeve 2-1-2 contacts the hydrogen storage unit 1, and the inner surface of the sleeve 2-1-2 cooperates with the fixing rod 2-2;

[0071] A plurality of bed supports 2-1 are fixed in series on the fixing rod 2-2, with gaps being left between the bed supports 2-1.

[0072] The gas supply system 3 is composed of a gas inlet and outlet 3-1, a filter 3-2, a gap space and a connecting pore; the gas supply system 3 is used to realize the gas exchange between the solid hydrogen storage material bed triggering area 1-1, the solid hydrogen storage material bed affected area 1-2 and the solid hydrogen storage initiating material and the outside,

[0073] A filter 3-2 is provided on the lower side of the gas inlet and outlet 3-1 to filter the gas entering and leaving the hydrogen storage tank.

[0074] The specific position and structure relationship of the housing 4 is as follows Figure 1 As shown, it consists of a hydrogen storage tank cylinder 4-1, a hydrogen storage tank end cover 4-2 and a sealing gasket 4-3.

[0075] The internal cavity of the hydrogen storage tank cylinder 4-1 accommodates the hydrogen storage unit 1, the triggering structure 2 and the gas supply system 3; the upper edge of the hydrogen storage tank cylinder 4-1 is provided with a cylinder flange connection hole 4-1-1; the bottom of the hydrogen storage tank cylinder 4-1 is fixed with a fixing rod 2-2;

[0076] The edge of the hydrogen storage tank end cover 4-2 is provided with an end cover flange connection hole 4-2-1; the hydrogen storage tank end cover 4-2 is provided with a gas inlet and outlet 3-1;

[0077] The cylinder flange connection hole 4-1-1 and the end cover flange connection hole 4-2-1 are connected by bolts; when the hydrogen storage tank cylinder 4-1 and the hydrogen storage tank end cover 4-2 are connected, a sealing gasket 4-3 is provided between the hydrogen storage tank cylinder 4-1 and the hydrogen storage tank end cover 4-2.

[0078] The temperature control device 5 is arranged outside the hydrogen storage tank cylinder 4-1 and uses a heat exchange fluid for heat exchange; the temperature control device 5 is used to remove the heat generated by the hydrogen absorption reaction of the solid hydrogen storage material.

[0079] Taking commercial Mg2Ni as a solid-state hydrogen storage functional material and commercial LaNi5 as a solid-state hydrogen storage initiation material as an example, a method for operating a high-temperature solid-state hydrogen storage device without external heat source startup includes the following steps:

[0080] Step 1, preparation before hydrogen absorption, first, fill the hydrogen storage unit in the hydrogen storage tank, fill the solid hydrogen storage initiation material in the initiation structure, then seal the hydrogen storage tank, perform vacuum operation to remove impurity gas in the hydrogen storage tank, and finally, start the temperature control device to achieve temperature control of the hydrogen storage tank;

[0081] The hydrogen storage unit is cylindrical, with a diameter of 15 cm and a height of 5 cm; the solid-state hydrogen storage functional material is commercial Mg2Ni, and the porosity of the hydrogen storage unit is 0.3;

[0082] In the initiation structure, the solid hydrogen storage initiation material is placed in a cylindrical partition plate; the partition plate has a diameter of 14 cm and a height of 0.5 cm; the solid hydrogen storage initiation material is commercial LaNi5, and the porosity of the solid hydrogen storage initiation material bed is 0.63;

[0083] The temperature control device uses a heat exchange fluid for heat exchange, the heat exchange fluid is thermal oil, and the heat transfer coefficient is 2000W / m 2 , the heat transfer fluid temperature is 298.15K.

[0084] Step 2, starting the hydrogen absorption process, first, hydrogen is introduced into the hydrogen storage tank through the gas supply system to make the hydrogen pressure reach the operating pressure; the hydrogen first reacts with the solid-state hydrogen storage initiating material to generate heat, thereby increasing the temperature of the solid-state hydrogen storage initiating material; then, the heat generated by the hydrogen absorption reaction of the solid-state hydrogen storage initiating material is transferred to the hydrogen storage unit, heating the triggering zone of the solid-state hydrogen storage material bed; finally, the reaction in the triggering zone of the solid-state hydrogen storage material bed releases a large amount of heat, driving the continuous reaction in the affected zone of the solid-state hydrogen storage material bed;

[0085] The operating pressure in the hydrogen storage tank is 4 MPa;

[0086] Step 3, control of the hydrogen absorption process, by adjusting the speed of the heat exchange fluid in the temperature control device to control the progress of the hydrogen absorption reaction in the trigger area of ​​the solid hydrogen storage material bed and the affected area of ​​the solid hydrogen storage material; after the hydrogen absorption reaction is completed or the control is completed, the gas supply system stops supplying gas, and at the same time, the temperature control device lowers the temperature of the hydrogen storage tank to room temperature.

[0087] In order to prove that the hydrogen storage device of the present invention can start and complete the hydrogen absorption process, the hydrogen storage tank startup and hydrogen absorption test was carried out. The test results are as follows Figure 3 As shown,

[0088] When the startup time is 25 seconds, the reaction fraction of the solid-state hydrogen storage functional material in the hydrogen storage tank increases rapidly, that is, the solid-state hydrogen storage functional material bed enters the continuous rapid reaction stage, which indicates that the hydrogen storage tank is successfully started;

[0089] When the reaction fraction of the solid hydrogen storage functional material bed in the hydrogen storage tank reaches 0.9, the time required is 870s;

[0090] During the startup process, the high-temperature solid-state hydrogen storage and hydrogen absorption process startup method of the present invention does not require external energy supply.

[0091] In order to demonstrate that the device and method of the present invention can achieve the effects of rapid startup and accelerated hydrogen absorption reaction, comparative example 1 is provided, which is a traditional heat exchange fluid startup method.

[0092] Comparative Example 1

[0093] A control method for a solid-state hydrogen storage device based on traditional heat exchange fluid activation, referred to as the traditional heat exchange fluid activation method, is described. Steps not specifically described are the same as those in Example 1, except that the triggering structure within the hydrogen storage tank is not used. Instead, the solid-state hydrogen storage functional material is heated using a heat exchange fluid within a temperature control device. Specifically, the temperature control device is activated to raise the temperature of the heat exchange fluid within the device to 393.15K. The temperature control device is then used to deliver the heat exchange fluid to the outer wall of the hydrogen storage tank to heat the tank, thereby activating the device. After the hydrogen storage tank is activated, the heat exchange fluid is maintained at 393.15K to remove heat generated during the hydrogen absorption process.

[0094] It is explained that due to the thermal resistance between the heat exchange fluid and the bed of solid hydrogen storage functional materials in the hydrogen storage tank, the temperature of the heat exchange fluid needs to be increased to 393.15K to meet the requirements of triggering the reaction; further, the temperature of the heat exchange fluid in the temperature control device needs to be maintained at 393.15K.

[0095] The test results of traditional hydrogen storage tank startup and hydrogen absorption, that is, the traditional heat exchange fluid startup method, are as follows Figure 3 As shown,

[0096] When the startup time is 13s, the reaction fraction of the solid hydrogen storage functional material bed in the hydrogen storage tank increases rapidly, that is, the solid hydrogen storage functional material bed enters the continuous rapid reaction stage, which indicates that the hydrogen storage tank is successfully started; however, since the temperature of the heat exchange fluid has been heated to 393.15K when the startup time is 0s, the actual startup time of the hydrogen storage tank should be Figure 3 The startup time shown in the figure plus the heat exchange fluid heating time is specifically 460s. Therefore, the startup time of the hydrogen storage tank under the traditional heat exchange fluid startup method is 473s. Compared with Example 1, it can be seen that the startup time increases by 1792%;

[0097] When the reaction fraction of the solid hydrogen storage functional material bed in the hydrogen storage tank reaches 0.9, the time required is 1950s. Compared with Example 1, the time required increases by 114%. The reason is that the temperature of the heat exchange fluid is maintained at 393.15K, resulting in a small temperature difference between the heat exchange fluid and the solid hydrogen storage functional material bed, and a slow heat transfer rate.

[0098] During startup, the energy consumption of the traditional heat exchange fluid startup method is 460kJ, and this figure does not take into account the energy dissipated during fluid flow. Compared with the high-temperature solid-state hydrogen storage and absorption process startup method of the present invention, the traditional heat exchange fluid startup method requires external energy supply.

[0099] In order to prove the universality of the startup method without external heat source of the present invention, Example 2 is provided, which is a high-temperature solid-state hydrogen storage device that is started without external heat source and in which the function of the triggering structure is realized by a fixed rod.

[0100] Example 2

[0101] A high-temperature solid-state hydrogen storage device that is activated without an external heat source, such as Figure 4 As shown, the parts not specifically described are the same as those in Example 1, except that: the fixed rod 2-2 replaces the partition plate 2-1-2 and is a hollow structure for loading solid-state hydrogen storage initiating material; accordingly, a connecting pore is provided on the fixed rod for hydrogen to enter the fixed rod and react with the solid-state hydrogen storage initiating material.

[0102] In order to prove that the hydrogen storage device in Example 2 of the present invention can start and complete the hydrogen absorption process, a hydrogen storage tank startup and hydrogen absorption test was carried out. The test results show that

[0103] When the startup time is 29 seconds, the reaction fraction of the solid hydrogen storage functional material bed in the hydrogen storage tank increases rapidly, that is, the solid hydrogen storage functional material bed enters the continuous rapid reaction stage, which indicates that the hydrogen storage tank is successfully started.

[0104] When the reaction fraction of the solid hydrogen storage functional material bed in the hydrogen storage tank reaches 0.9, the time required is 912s;

[0105] During the startup process, the high-temperature solid-state hydrogen storage and hydrogen absorption process startup method of the present invention does not require external energy supply.

[0106] Example 2 shows that the effect of starting without an external heat source can also be achieved by using a hollow fixed rod filled with solid hydrogen storage initiation material as an initiation structure.

Claims

1. A high-temperature solid-state hydrogen storage tank that can be started without an external heat source, characterized in that: It consists of a hydrogen storage unit, an initiating structure, a gas supply system, a shell and a temperature control device; The hydrogen storage unit consists of a solid hydrogen storage material bed triggering area and a solid hydrogen storage material bed swept area; The initiation structure consists of solid hydrogen storage initiation material, bed support and fixing rod; The gas supply system consists of gas inlets and outlets, filters, interstitial spaces and connecting pores; The outer shell is composed of a hydrogen storage tank cylinder, a hydrogen storage tank end cover and a sealing gasket; The temperature control device uses a heat exchange fluid to exchange heat.

2. The high-temperature solid-state hydrogen storage tank according to claim 1, characterized in that: In the hydrogen storage unit, the solid-state hydrogen storage material bed triggering zone and the solid-state hydrogen storage material affected zone are both composed of solid-state hydrogen storage functional material particles and pores; the solid-state hydrogen storage functional material is a large-capacity solid-state hydrogen storage material; One side of the solid hydrogen storage material bed triggering zone is connected to the bed support in the triggering structure, and the other side is connected to the solid hydrogen storage material bed affected area; the distance from the solid hydrogen storage material bed triggering zone to the bed support is 0-15mm; A gap space is left between the hydrogen storage unit and the side wall of the hydrogen storage tank cylinder in the shell and the upper and lower walls of the hydrogen storage tank.

3. The high-temperature solid-state hydrogen storage tank according to claim 1, characterized in that: In the initiation structure, the solid-state hydrogen storage initiation material is a low-temperature solid-state hydrogen storage material; The bed support is composed of a partition plate and a sleeve; The partition plate is fixed at the bottom of the sleeve, and the upper side of the partition plate contacts the triggering area of ​​the solid hydrogen storage material bed; The outer surface of the sleeve contacts the hydrogen storage unit, and the inner surface of the sleeve matches the fixing rod; At least one of the partition plates of the fixed rod and the bed support is a hollow structure for loading a solid hydrogen storage initiating material; when the fixed rod or the bed support is loaded with the solid hydrogen storage initiating material, the fixed rod or the bed support is provided with a connecting pore for hydrogen to enter the fixed rod or the bed support and react with the solid hydrogen storage initiating material; the mass of the solid hydrogen storage initiating material bed does not exceed 1 / 2 of the mass of the solid hydrogen storage functional material in the hydrogen storage unit; A plurality of bed supports are fixed in series on the fixing rod, with gaps between the bed supports.

4. The high-temperature solid-state hydrogen storage tank according to claim 1, characterized in that: In the gas supply system, a filter is provided at the lower side of the gas inlet and outlet for filtering the gas entering and exiting the hydrogen storage tank.

5. The high-temperature solid-state hydrogen storage tank according to claim 1, characterized in that: In the shell, the inner cavity of the hydrogen storage tank cylinder accommodates the hydrogen storage unit, the triggering structure and the gas supply system; the upper edge of the hydrogen storage tank cylinder is provided with a cylinder flange connection hole; and the bottom of the hydrogen storage tank cylinder is fixed with a fixing rod; The edge of the hydrogen storage tank end cover is provided with an end cover flange connection hole; the end cover of the hydrogen storage tank is provided with a gas inlet and outlet; The cylinder flange connection hole and the end cover flange connection hole are connected by bolts; when the hydrogen storage tank cylinder and the hydrogen storage tank end cover are connected, a sealing gasket is provided between the hydrogen storage tank cylinder and the hydrogen storage tank end cover.

6. The high-temperature solid-state hydrogen storage tank according to claim 1, characterized in that: In the temperature control device, the temperature control device is arranged outside the cylinder of the hydrogen storage tank and is used to take away the heat generated by the hydrogen absorption reaction of the solid hydrogen storage material.

7. A method for operating a high-temperature solid-state hydrogen storage tank without external heat source startup, characterized in that The following steps are involved: Step 1, preparation before hydrogen absorption, first, fill the hydrogen storage unit in the hydrogen storage tank, fill the solid hydrogen storage initiation material in the initiation structure, then seal the hydrogen storage tank, perform vacuum operation to remove impurity gas in the hydrogen storage tank, and finally, start the temperature control device to achieve temperature control of the hydrogen storage tank; Step 2, starting the hydrogen absorption process, first, hydrogen is introduced into the hydrogen storage tank through the gas supply system to make the hydrogen pressure reach the operating pressure; the hydrogen first reacts with the solid-state hydrogen storage initiating material to generate heat, thereby increasing the temperature of the solid-state hydrogen storage initiating material; then, the heat generated by the hydrogen absorption reaction of the solid-state hydrogen storage initiating material is transferred to the hydrogen storage unit, heating the triggering zone of the solid-state hydrogen storage material bed; finally, the reaction in the triggering zone of the solid-state hydrogen storage material bed releases a large amount of heat, driving the continuous reaction in the affected zone of the solid-state hydrogen storage material bed; Step 3, control of the hydrogen absorption process, by adjusting the speed of the heat exchange fluid in the temperature control device to control the progress of the hydrogen absorption reaction in the trigger area of ​​the solid hydrogen storage material bed and the affected area of ​​the solid hydrogen storage material; after the hydrogen absorption reaction is completed or the control is completed, the gas supply system stops supplying gas, and at the same time, the temperature control device lowers the temperature of the hydrogen storage tank to room temperature.

8. The method for operating a high-temperature solid-state hydrogen storage tank according to claim 7, wherein: When the solid-state hydrogen storage functional material is Mg2Ni and the solid-state hydrogen storage initiating material is LaNi5, In step 1, the hydrogen storage unit is cylindrical, with a diameter of 15 cm, a height of 5 cm, and a porosity of 0.3; In the initiation structure, the solid hydrogen storage initiation material is placed in a cylindrical partition plate; the partition plate has a diameter of 14 cm and a height of 0.5 cm, and the porosity of the solid hydrogen storage initiation material bed is 0.63; The temperature control device uses heat exchange fluid, the heat exchange fluid is thermal oil, and the heat transfer coefficient is 200-5000W / m 2 , the heat transfer fluid temperature is 288.15-308.15K; In step 2, the operating pressure in the hydrogen storage tank is 1-5 MPa.

Images