CN-120667637-B - High-temperature solid-state hydrogen storage device without external heat source start and operation method thereof

CN120667637BCN 120667637 BCN120667637 BCN 120667637BCN-120667637-B

Abstract

The invention discloses a high-temperature solid-state hydrogen storage device without external heat source starting, which 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, wherein the hydrogen storage unit consists of a solid hydrogen storage material bed triggering area and a solid hydrogen storage material bed sweep area, the initiating structure consists of a solid hydrogen storage initiating material, a bed support and a fixed rod, the gas supply system consists of a gas inlet and outlet, a filter screen, a clearance space and a communication pore, the shell consists of a hydrogen storage tank body, a hydrogen storage tank end cover and a sealing gasket, and the temperature control device adopts heat exchange fluid for heat exchange. The operation method of the high-temperature solid-state hydrogen storage device without external heat source starting comprises the following steps of 1, preparing before hydrogen absorption, 2, starting a hydrogen absorption process, and 3, controlling the hydrogen absorption process.

Inventors

YAO JING
LI QIAN
HU BIN

Assignees

重庆大学
重庆新型储能材料与装备研究院

Dates

Publication Date: 20260508
Application Date: 20250710

Claims (8)

1. The high-temperature solid hydrogen storage tank without external heat source start is characterized by comprising a hydrogen storage unit, an initiation 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 sweep area, wherein the solid hydrogen storage material bed triggering area and the solid hydrogen storage material sweep area in the hydrogen storage unit are both composed of solid hydrogen storage functional material particles and pores, the solid hydrogen storage functional material is a high-capacity solid hydrogen storage material; the initiation structure consists of a solid hydrogen storage initiation material, a bed support and a fixing rod, wherein the solid hydrogen storage initiation material in the initiation structure is a low-temperature solid hydrogen storage material; The bed support consists 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 is contacted with the solid hydrogen storage material bed triggering area; the outer surface of the sleeve is contacted with the hydrogen storage unit, and the inner surface of the sleeve is matched with the fixed rod; When the solid hydrogen storage initiating material is filled in the fixed rod or the bed support, the fixed rod or the bed support is provided with a communicating pore for hydrogen to enter the fixed rod or the bed support and react with the solid hydrogen storage initiating material; The gas supply system consists of a gas inlet and outlet, a filter screen, a clearance space and a communication pore; The shell consists of a hydrogen storage tank cylinder, a hydrogen storage tank end cover and a sealing gasket, wherein a cavity in the hydrogen storage tank cylinder is used for accommodating a hydrogen storage unit, an initiation structure and an air supply system; The temperature control device adopts heat exchange fluid for heat exchange.
2. The high temperature solid hydrogen storage tank of claim 1 wherein the solid hydrogen storage material bed triggering area is 0-15 mm to the bed support.
3. The high-temperature solid hydrogen storage tank of claim 1, wherein the mass of the solid hydrogen storage initiation material bed is not more than 1/2 of the mass of the solid hydrogen storage functional material in the hydrogen storage unit; the bed supports are serially connected and fixed on the fixing rod, and a gap space is reserved between the bed supports.
4. The high-temperature solid hydrogen storage tank of claim 1, wherein a filter screen is arranged at the lower side of the gas inlet and outlet in the gas supply system for filtering gas entering and exiting the hydrogen storage tank.
5. The high-temperature solid hydrogen storage tank as claimed in claim 1, wherein the upper edge of the hydrogen storage tank is provided with a tank flange connecting hole; the edge of the hydrogen storage tank end cover is provided with an end cover flange connecting hole; when the hydrogen storage tank body is connected with the hydrogen storage tank end cover, a sealing gasket is arranged between the hydrogen storage tank body and the hydrogen storage tank end cover.
6. The high-temperature solid hydrogen storage tank as set forth in claim 1, wherein the temperature control device is arranged outside the hydrogen storage tank body and is used for taking away heat generated by the hydrogen absorption reaction of the solid hydrogen storage material.
7. A method of operating a high temperature solid state hydrogen storage tank without external heat source activation using the high temperature solid state hydrogen storage tank without external heat source activation of any one of claims 1-6, the method comprising the steps of: Step 1, preparing before hydrogen absorption, firstly filling a hydrogen storage unit in a hydrogen storage tank, filling a solid hydrogen storage initiating material in an initiating structure, then sealing the hydrogen storage tank, performing vacuumizing operation to remove impurity gas in the hydrogen storage tank, and finally starting a temperature control device to control the temperature of the hydrogen storage tank; Step 2, starting a hydrogen absorption process, namely firstly introducing hydrogen into a hydrogen storage tank through a gas supply system to enable the hydrogen pressure to reach the operating pressure, reacting the hydrogen with a solid hydrogen storage initiating material to generate heat so as to increase the temperature of the solid hydrogen storage initiating material, then transferring the heat generated by the hydrogen absorption reaction of the solid hydrogen storage initiating material to a hydrogen storage unit to heat a solid hydrogen storage material bed triggering area, and finally, reacting the solid hydrogen storage material bed triggering area to release a large amount of heat so as to drive the solid hydrogen storage material bed sweep area to continuously react; And 3, controlling the hydrogen absorption process, namely controlling the progress of hydrogen absorption reaction between the solid hydrogen storage material bed triggering area and the solid hydrogen storage material wave-over area by adjusting the speed of heat exchange fluid in the temperature control device, stopping air supply by the air supply system after the hydrogen absorption reaction is finished or after the control is finished, and simultaneously reducing the temperature of the hydrogen storage tank to room temperature by the temperature control device.
8. The method of operating a high temperature solid state hydrogen storage tank as claimed in claim 7, wherein when the solid state hydrogen storage functional material is Mg 2 Ni and the solid state hydrogen storage initiating material is LaNi 5 , In the step 1, the hydrogen storage unit is cylindrical, the diameter is 15 cm, the height is 5 cm, and the porosity is 0.3; In the initiation structure, solid hydrogen storage initiation material is arranged in a cylindrical partition plate, the diameter of the partition plate is 14 cm, the height is 0.5 cm, and the porosity of the solid hydrogen storage initiation material bed layer is 0.63; The temperature control device adopts heat exchange fluid for heat exchange, the heat exchange fluid is heat conduction oil, the heat exchange coefficient is 200-5000W/m 2 , and the temperature of the heat exchange fluid is 288.15-308.15K; In the step 2, the operating pressure in the hydrogen storage tank is 1-5 MPa.

Description

High-temperature solid-state hydrogen storage device without external heat source start and operation method thereof Technical Field The invention belongs to the field of hydrogen energy storage and transportation, and particularly relates to a high-temperature solid-state hydrogen storage device started without an external heat source and an operation method thereof. Background When the solid-state hydrogen storage material is applied in a laboratory, only a small amount of solid-state hydrogen storage material is used, the temperature of a solid-state hydrogen storage material bed is raised simply and quickly, but in practical application, the conventional high-temperature solid-state hydrogen storage device has the problems of high temperature raising difficulty and long time of the solid-state hydrogen storage material bed due to large mass and small heat conductivity coefficient of the solid-state hydrogen storage material, and the conventional solid-state hydrogen storage device adopts a traditional heat exchange fluid starting method, namely the whole medium-high-temperature solid-state hydrogen storage material bed is heated to a higher temperature through heat exchange fluid, and then hydrogen is introduced to perform hydrogen absorption reaction. For example, prior literature 1(Large scale magnesium hydride tank coupled with an external heat source,International Journal of Hydrogen Energy,2012,37:9103-9111) uses high temperature conduction oil to heat a MgH 2 bed to around 240 ℃ and then performs a hydrogen absorption operation. And in the subsequent hydrogen absorption reaction process, the temperature of the heat conduction oil is also maintained at about 240 ℃ and is used for taking away a large amount of heat generated by the hydrogen absorption reaction. However, such a starting method based on heat exchange fluid has the following 2 technical problems: 1. Because the heat exchange fluid is adopted, the required heat exchange fluid has the basic characteristics of large specific heat capacity and large volume, the problems of high required energy consumption and long heating time exist in the heating process, which are simply referred to as energy consumption-time problems, and in the specific prior document 1, the starting time of the hydrogen absorption reaction of the solid hydrogen storage material bed layer is 2 hours; 2. Because the heat exchange fluid is adopted, the heat management system needs to realize the temperature rising function and the temperature reducing function at the same time, so that after the starting process is finished, the heat exchange fluid is in a high-temperature state, and meanwhile, because the heat exchange fluid has a large specific heat capacity, the temperature of the heat exchange fluid is slowly reduced, the heat exchange efficiency of the heat exchange fluid is directly reduced in the subsequent hydrogen absorption reaction process, the problem of low temperature reducing efficiency is finally caused, and the reaction temperature cannot be controlled in time, which is simply called the temperature control problem. To solve the above problem 1 of power consumption-time, the thermal management system may employ an electrical heating means. For example, the prior document 2(Experimental and numerical study of a magnesium hydride tank,International Journal of Hydrogen Energy,2010,35:6311-6322) uses a heating coil wound around the outer wall surface of a hydrogen storage tank filled with MgH 2 material, heats the material bed to 300 ℃ by the heating coil, and then performs a hydrogen absorbing operation. But the problem of this solution consists of 2 aspects: 1. The electric heating coil is arranged outside the hydrogen storage device, so that the heating distance from the electric heating coil to the center of the solid hydrogen storage material bed layer is long, and a heat preservation device is additionally arranged outside the heating coil; 2. The electric heating coil is required to heat the whole medium-high temperature solid hydrogen storage material bed, and the energy consumption required by heating is increased in proportion to the mass of the heated solid hydrogen storage material; the 2 problems mentioned above have resulted in the problem that the start-up time and the energy consumption cannot be effectively reduced, and the start-up time of the existing document 2 still needs more than 1h. In addition, the problem 2 of the prior document 2 is still unable to be effectively solved, and the temperature control problem of the prior document 1 is still unable to be effectively solved, because the prior document 2 adopts an electric heating coil as a heating system, namely, a heat exchange fluid is not needed, but adopts a technical scheme of arranging cooling air in the hydrogen storage device for cooling, but because the cooling air is arranged in the hydrogen storage device, the problem of small heat exchange area exists, heat generated by the