CN-121977161-A - Vehicle-mounted high-mass-density hydrogen storage device and application thereof

CN121977161ACN 121977161 ACN121977161 ACN 121977161ACN-121977161-A

Abstract

The invention discloses a vehicle-mounted high-quality density hydrogen storage device and application thereof, wherein a tubular hydrogen storage unit is formed by filling a weak adsorption effect hydrogen storage material in a tubular reactor, and a plurality of tubular reactors are arranged in parallel to form the high-quality density hydrogen storage device; meanwhile, the tubular reactor is taken as a tube side, the outer shell of the hydrogen storage device is set as a shell side, and a heat exchange medium is introduced into the shell side to enable the hydrogen storage module to be in a set and uniform temperature field, so that the thermal management of the hydrogen absorption/desorption process is enhanced, and stable hydrogen storage and supply are realized. The invention utilizes the characteristics of relatively mild thermal effect caused by high-quality density hydrogen storage potential and lower enthalpy change of the weak adsorption effect hydrogen storage material, effectively reduces the temperature difference and thermal management burden of a bed layer, combines the material forming filling and heat conduction enhancement modes, reduces the heat and mass transfer resistance of the bed layer, realizes stable hydrogen storage and supply under low-temperature hydrogen absorption and medium-temperature hydrogen release windows, has compact structure, can realize modularized expansion, is convenient to maintain, and is suitable for vehicle-mounted hydrogen supply scenes.

Inventors

LIANG FEI
REN QUANBING
ZHANG CHUNQI
LIU XUEWU
YANG QINGQING
LI WENLONG
WANG YIJING
LIU YIPENG
FENG LAN
ZHENG BO

Assignees

安徽大学
江西江钨浩运科技有限公司
南开大学

Dates

Publication Date: 20260505
Application Date: 20260210

Claims (9)

1. A vehicle-mounted high-quality-density hydrogen storage device is characterized in that a tubular reactor (4) is adopted to form a tubular hydrogen storage unit based on a weak adsorption effect hydrogen storage material (2), the tubular reactor (4) is filled with the weak adsorption effect hydrogen storage material (2), a plurality of tubular reactors (4) are arranged in parallel, two ends of the device are connected through a left end plate (1) and a right end plate (9) to form a closed end part, a high-quality-density hydrogen storage device is formed, a port header pipe (5 b) communicated with all reactor ports (4 a) is used as a hydrogen filling port (5 a) of the hydrogen storage device, the tubular reactor (4) is used as a tube side, a shell side of the hydrogen storage device is used as a shell side, a heat exchange medium is introduced into the shell side, a hydrogen storage module is positioned in a set and uniform temperature field to strengthen the heat management of a hydrogen absorption/release process, and two ports led out from the outer shell of the hydrogen storage module are respectively used as a heat exchange medium inlet (3 a) and a heat exchange medium outlet (3 b).
2. The vehicle-mounted high-mass-density hydrogen storage device according to claim 1, wherein a central conduit (4 b) is axially arranged in the tubular reactor (4), the weak adsorption effect hydrogen storage material (2) is filled in an annular region at the periphery of the central conduit (4 b), the central conduit (4 b) forms an airflow channel, the central conduit (4 b) is used for axially distributing hydrogen and diffusing the hydrogen to the annular region, a plurality of heat conducting separation plates (4 c) are circumferentially arranged at intervals in the annular region of the weak adsorption effect hydrogen storage material filled in the tubular reactor (4), the heat conducting separation plates (4 c) arranged at intervals are used for enhancing heat conduction of a bed layer and improving uniformity of temperature and mass transfer in the hydrogen adsorption and desorption process, a filter plate (4 d) is arranged at the left end of the central conduit (4 b) of the tubular reactor tube (4) and is a sintered metal filter plate, a stainless steel filter screen or a metal fiber felt and used for inhibiting pulverized particles from entering the airflow channel and blocking the airflow channel, a temperature sensor (10) is arranged at the right end of the tubular reactor tube (4) and is communicated with the annular region, and a temperature sensor (11) is arranged at the right end of the tubular reactor tube (4) and is inserted into a temperature sensor (11) and a temperature sensor (11) is arranged at the temperature sensor.
3. The vehicle-mounted high-quality-density hydrogen storage device according to claim 1, wherein reactor ports (4 a) of all the tubular reactors (4) arranged in parallel are supported by a left end plate (1) to form a left end and are communicated with a port main pipe (5 b), the other ends of all the tubular reactors (4) are supported by a right end plate (9) to form a right end, a port pressure sensor (5 c) is arranged in the port main pipe (5 b), a right end cover (8) is arranged on the outer side of the right end plate (9), and a longitudinal pull rod (7) is arranged between the left end plate (1) and the right end plate (9) to form a detachable frame of the hydrogen storage device.
4. The vehicle-mounted high-quality-density hydrogen storage device according to claim 1, wherein the heat exchange medium inlet (3 a) and the heat exchange medium outlet (3 b) are both positioned at one end of a left end plate with the reactor port (4 a), the heat exchange medium inlet (3 a) and the heat exchange medium outlet (3 b) are positioned at the opposite angles of the left end plate (1), the heat exchange medium outlet (3 b) is connected with a lead-out pipe section, the pipe end of the lead-out pipe section reaches one end of a right end plate (9), a plurality of baffle plates (6) are arranged in the shell pass, and the baffle plates (6) are used as support plates of the tubular reactor (4).
5. The vehicle-mounted high-mass-density hydrogen storage device according to claim 1, wherein the plurality of tubular reactors (4) are arranged in a single-layer tiling mode or a multi-layer stacking mode so as to match the appearance requirements of different vehicle-mounted installation spaces.
6. The vehicle-mounted high-quality-density hydrogen storage device according to claim 1, wherein the weak adsorption effect hydrogen storage material is one or more of MXene layered materials, metal-organic framework materials MOFs and covalent organic framework materials COFs, and is powder, a sheet-shaped body or a block-shaped body, and the sheet-shaped body or the block-shaped body is formed by cold pressing of the powder.
7. The device of claim 1, wherein the weakly adsorbed hydrogen storage material is compounded with a thermally conductive filler, wherein the thermally conductive filler is one or more of expanded graphite, metal ribs or metal foam, and is used for improving the effective thermal conductivity of the material bed and inhibiting the temperature difference of the bed.
8. A vehicle-mounted high-mass-density hydrogen storage system is characterized in that a peripheral pipeline is arranged for the vehicle-mounted high-mass-density hydrogen storage device as claimed in claim 1 to form the hydrogen storage system, and the peripheral pipeline comprises: The hydrogen charging and discharging pipeline comprises a hydrogen charging and discharging main pipe communicated with a hydrogen charging and discharging port (5 a), and a hydrogen charging branch pipe and a hydrogen discharging branch pipe communicated with the hydrogen charging and discharging main pipe, wherein a main pipe pressure sensor (15) and a main pipe valve (16) are respectively arranged in the hydrogen charging and discharging main pipe, a hydrogen charging valve (18), a hydrogen charging flow meter (20), a hydrogen charging branch valve (22), a hydrogen charging pressure reducing valve (23) and a hydrogen charging inlet valve (26) are sequentially arranged from one end of the hydrogen charging and discharging main pipe in the hydrogen charging branch pipe, and a hydrogen placing inlet valve (19), a buffer tank (21), a hydrogen discharging flow meter (24), a hydrogen discharging pressure reducing valve (25) and a hydrogen discharging valve (27) are sequentially arranged from one end of the hydrogen charging and discharging main pipe in the hydrogen discharging branch pipe; A heat exchange medium pipeline which is communicated with the shell side through the heat exchange medium inlet (3 a) and the heat exchange medium outlet (3 b) to form a heat exchange medium circulation loop, wherein a heat exchange medium pump (12), a heat exchange medium inlet valve (13), a heat exchanger (14) and a heat exchange medium outlet valve (17) are respectively arranged in the heat exchange medium pipeline and are used for realizing circulation, cooling or heating of a heat exchange medium; The replacement pipeline is a replacement pipe connected to a hydrogen discharge branch pipe between a hydrogen discharge pressure reducing valve (25) and a hydrogen discharge valve (27), the replacement pipe is communicated with a vacuum pump (29), and a replacement valve (28) is arranged in the replacement pipe and is used for vacuumizing, inerting replacement or emptying the hydrogen charging and discharging pipeline and the tubular reactor (4).
9. A control method of a vehicle-mounted high-mass-density hydrogen storage system is characterized in that aiming at the vehicle-mounted high-mass-density hydrogen storage system as claimed in claim 8, the hydrogen charging and discharging control is carried out according to the following method: before hydrogen charging control is carried out, firstly, a replacement valve (28) is opened, and a vacuum pump (29) is utilized to pretreat the tubular reactor and a hydrogen charging and discharging pipeline, wherein the pretreatments are evacuation treatment, vacuumizing treatment or inert gas replacement treatment; setting a heat exchange medium circulation loop as a cooling working condition to keep the temperature of a bed layer within a set hydrogen charging temperature range of-30 ℃ to 0 ℃, establishing a hydrogen charging channel for a tubular reactor by a hydrogen charging branch pipe and a hydrogen charging and discharging main pipe, wherein the tubular reactor is in a hydrogen charging state, establishing hydrogen charging pressure by utilizing a hydrogen charging pressure reducing valve (23), and carrying out linkage adjustment on the main pipe valve (16), the hydrogen charging valve (18), the hydrogen charging branch valve (22) and a hydrogen charging inlet valve (26) according to detection signals of a pressure sensor (15) and a hydrogen charging flowmeter (20) to ensure that the pressure of the bed layer steadily rises and hydrogen charging is stopped when the target hydrogen charging pressure is reached; the hydrogen discharge control comprises the steps of setting a heat exchange medium circulation loop as a heating working condition, keeping the temperature of a bed layer within a hydrogen discharge set temperature range of 60-90 ℃, establishing a hydrogen discharge channel for a tubular reactor by a hydrogen charging and discharging main pipe and a hydrogen discharge branch pipe, outputting hydrogen with set pressure to a hydrogen end by utilizing a hydrogen discharge pressure reducing valve (25), and carrying out linkage adjustment on a main pipe valve (16), a hydrogen discharge inlet valve (19) and a hydrogen discharge valve (27) according to detection signals of a pressure sensor (15) and a hydrogen discharge flowmeter (24) to realize stable hydrogen supply.

Description

Vehicle-mounted high-mass-density hydrogen storage device and application thereof Technical Field The invention belongs to the technical field of hydrogen energy storage and vehicle-mounted hydrogen supply, and particularly relates to a vehicle-mounted high-quality density hydrogen storage device and application thereof, in particular to a device structure matching, heat and mass transfer enhancement and vehicle-mounted vibration resistance design and control method for taking low-enthalpy and high-capacity weak adsorption effect hydrogen storage materials such as MXene layered materials, metal organic framework Materials (MOFs), covalent organic framework materials (COFs) and the like as hydrogen storage media. Background Under the promotion of the low carbonization trend of the 'double carbon' target and the traffic terminal, hydrogen energy is regarded as an important secondary energy source because of cleanness, high efficiency and wide source. Applications such as hydrogen fuel cell vehicles put forward the comprehensive requirements of "high safety, high energy density, fast response, wide temperature range adaptation" for hydrogen supply systems. In the prior art, the high-pressure gaseous hydrogen storage is mature, the pressure is high, the compression energy consumption is high, the safety risk is outstanding, the low-temperature liquid hydrogen storage is high in density, but a-253 ℃ cryogenic and complex heat insulation system is needed, the energy consumption and the cost are high, the volatilization loss exists, and the vehicle-mounted long-term stable use is not facilitated. Therefore, the solid-state hydrogen storage has the advantages of high volume density, high purity of hydrogen release, good safety and the like, and becomes an important direction of vehicle-mounted high-safety hydrogen supply. The engineering at present adopts more solid routes mainly comprising metal hydrides/hydrogen storage alloys, but has the prominent bottlenecks that the hydrogen absorption/desorption reaction is often accompanied by obvious heat release/heat absorption, the temperature fluctuation of a bed layer is obvious due to larger enthalpy change, the intrinsic thermal conductivity of the material is limited, so that the heat is difficult to timely lead out or supply, further, the temperature gradient is formed, the dynamics is obviously inhibited, the hydrogen absorption/desorption rate is slow, the cold start time is long, and the effective capacity is reduced. Meanwhile, partial alloy has volume expansion and pulverization in circulation, which is easy to cause mass transfer resistance rise, air guide channel blockage and container thermal stress concentration, and affects safety and overhaulability. In order to improve heat exchange, the fin adding mode occupies a material filling space, reduces the volume hydrogen storage density, and the thin-wall pipeline and the welding position have failure risks under the working conditions of pulverization extrusion and vibration. Different from the alloy route, the novel high-capacity hydrogen storage materials such as MXene layered materials, metal organic framework Materials (MOFs), covalent organic framework materials (COFs) and the like are based on layered/porous structures, and the hydrogen storage mechanism is more biased to a reversible weak adsorption effect, so that the novel high-capacity hydrogen storage material has the potential advantages that firstly, under reasonable structural design and pore-forming regulation and control, the material can achieve a higher-quality hydrogen storage density target, has the potential of light weight and high capacity, secondly, the heat release and heat absorption strength in the hydrogen absorption/desorption process are relatively weakened due to relatively mild adsorption effect and low equivalent enthalpy change, and is beneficial to reducing the thermal management burden, reducing the temperature difference of a bed layer and improving the quick response capability. This means that if the material advantages of MXene layered materials, organometallic framework Materials (MOFs) and covalent organic framework materials (COFs) can be combined with the integrated design of the heat and mass transfer structure for vehicle-mounted applications, it is possible to achieve a more efficient, stable hydrogen storage and supply process at a lower temperature window. However, engineering of MXene layered materials, metal organic framework Materials (MOFs) and covalent organic framework materials (COFs) still faces the dual challenges of thermal mass coupling and on-board reliability, namely, on one hand, porous/layered materials still suffer from coupling effects of porosity, packing density, gas distribution and heat transfer paths in the bed, and if the structure is improperly designed, local temperature differences and mass transfer bottlenecks can still occur, and on the other hand, on-board working conditions requir