A hydrogen energy storage system

Abstract

The present application relates to hydrogen energy storage device technical field, specifically point to a kind of hydrogen energy storage system, including shell and hydrogen energy supply module, the storage system further include by inside to outside coaxially nested in shell inside storage module, compensation module and heat management module;Heat management module side is provided with circulation module, the inner bag of storage module is provided with corrugated structure, heat when hydrogen absorption / hydrogen release is dynamically heat managed by multilayer nested heat exchange, limiting composite structure, also by setting circulation module in shell to control suitable heat exchange path, not only solve the reaction efficiency fluctuation problem caused by heat accumulation or insufficient supply of traditional solid-state hydrogen storage device, also by shortening or lengthening path length optimization heat exchange efficiency, reduce energy loss.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of hydrogen energy storage devices, in particular to a hydrogen energy storage system. BACKGROUND

[0002] As the most potential clean secondary energy in the 21st century, hydrogen energy has become an important direction of global energy transformation due to its high combustion heat value, wide sources and various utilization forms.

[0003] However, the low density characteristics of hydrogen gas lead to significant technical bottlenecks in the storage and transportation process, which seriously restricts the industrialization application process. The current mainstream hydrogen storage technologies include high-pressure gaseous hydrogen storage, low-temperature liquid hydrogen storage and solid-state material hydrogen storage. For example, the existing hydrogen storage alloy produces a powder phenomenon caused by the lattice volume change in the hydrogen absorption and desorption process, and the resulting bed body heat conduction performance degradation and stress concentration problem have become an important factor restricting the service life and safety of the device.

[0004] In addition, there are complex multi-physical field coupling effects in the working process of the solid-state hydrogen storage device: the dynamic thermal management requirements of hydrogen absorption and desorption heat release and hydrogen desorption heat absorption, the mass transfer resistance between hydrogen flow field and porous medium, and the flow accumulation of alloy powder due to volume effect, which form a vicious cycle. SUMMARY

[0005] The main purpose of the present application is to provide a hydrogen energy storage system, which aims to solve the problem that the existing solid-state hydrogen storage device cannot meet the dynamic thermal management requirements of heat absorption and desorption.

[0006] To achieve the above purpose, the present application provides a hydrogen energy storage system, which comprises a shell and a hydrogen energy supply module, and further comprises a storage module, a compensation module and a thermal management module coaxially nested in the shell from inside to outside;

[0007] The side of the thermal management module is provided with a circulation module, the inner container of the storage module is provided with a corrugated structure, the compensation module comprises a compensation structure wound on the outer periphery of the corrugated structure, the shell is provided with a first liquid port, a second liquid port and a third liquid port, and the thermal management module is provided with a plurality of flow channels communicating with the first liquid port and the second liquid port;

[0008] The circulation module communicates with a plurality of flow channels, and the circulation module comprises a control unit, which manages the thermal management path of the storage system by adjusting the opening and closing of the first liquid port, the second liquid port and the third liquid port. When hydrogen is absorbed, the first liquid port and the third liquid port are opened, and the second liquid port is closed. When hydrogen is desorbed, the first liquid port and the second liquid port are opened, and the third liquid port is closed.

[0009] Optionally, the flow channels include pipes spirally wound on the outer periphery of the compensation structure, the openings of the pipes are respectively communicated with the first liquid port, the second liquid port, and the third liquid port is arranged on one side close to the circulation module, and the circulation module is movably arranged in the shell.

[0010] Optionally, the circulation module includes a base, a circulating member movably arranged in the base, and a rotating drum arranged in the circulating member, the circulating member is an axisymmetric structure, and the symmetric sides of the circulating member include rotating rings movably arranged with the rotating drum, and the rotating rings are also movably arranged in the base.

[0011] Optionally, the rotating drum is provided with a plurality of through holes, the side of the rotating ring close to the rotating drum is provided with a plurality of openings, the base is provided with a connecting frame, and the rotating drum and the rotating ring are movably arranged on the base through the connecting frame and are communicated on the symmetric sides through the through holes and the openings.

[0012] Optionally, the plurality of through holes and openings are obliquely arranged.

[0013] Optionally, the corrugated structure includes a compensation metal for providing a telescopic compensation capability, the compensation metal includes 58-63wt% of Ni, 20-23wt% of Cr, 8-10wt% of Mo, and 3.15-4.15wt% of Nb.

[0014] Optionally, the storage module is provided with a hydrogen storage metal for hydrogen storage, and the hydrogen storage metal has a composition of Awt% of Ti a Mn b Cr c V d Zr e Fe f , Bwt% of La x Ni y , and Cwt% of V, wherein a, b, c, d, e, f, x and y are molar ratios; 0.75≤a≤0.92; 1.3≤b≤1.8; 0.3≤c≤0.6; 0.15≤d≤0.4; 0.05≤e≤0.2; 0.01≤f≤0.1; 75≤A≤90; 5≤B≤15; 3≤C≤10; 0.95≤x≤1.05; 4.85≤y≤5.15.

[0015] Optionally, the compensation structure includes 60-65wt% of carbon fibers and 35-40wt% of an epoxy resin matrix.

[0016] Optionally, the composition of the hydrogen storage metal satisfies:

[0017] a+e=0.8-1.05;

[0018] b+c+d=1.8-2.2.

[0019] Optionally, the storage system comprises a heat exchanger thermally coupled to the thermal management path.

[0020] The hydrogen energy storage system provided by the embodiment of the present application dynamically manages the heat during hydrogen absorption and hydrogen release through the multi-layer nested heat exchange and the limiting composite structure, and controls the appropriate heat exchange path by arranging a circulating module in the shell. It can be understood that the first liquid port, the second liquid port and the third liquid port are connected with numerical control valves and communicate with the cooling pipeline through the numerical control valves. The circulating module and the thermal management module form a dynamic cooling / heat storage path in the shell. For the cooling path, the first liquid port and the third liquid port are opened, and the second liquid port is closed. At this time, the flow distance of the cooling path in the shell is the shortest, which helps the thermal management module to absorb the heat generated during the hydrogen absorption process of the storage module, and to exchange heat with the external cooling pipeline at the fastest speed, thereby realizing the heat management of the hydrogen absorption process. Not only does it solve the problem of reaction efficiency fluctuation caused by heat accumulation or insufficient supply in traditional solid-state hydrogen storage devices, but also optimizes the heat exchange efficiency by shortening or lengthening the path length, thereby reducing energy loss. In addition, the pipeline designed to be spirally wound around the outer periphery of the compensation structure further strengthens the contact area of the flow channel and the compensation structure, and improves the uniformity and response speed of heat conduction. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 It is a structural schematic diagram of the system of the present application;

[0022] Figure 2 It is a structural schematic diagram of the system of the present application;

[0023] Figure 3 It is a structural schematic diagram of the system of the present application;

[0024] Reference signs:

[0025] 1 - shell, 2 - circulating module, 3 - storage module, 4 - compensation module, 5 - thermal management module;

[0026] 11 - first liquid port, 12 - second liquid port, 13 - third liquid port;

[0027] 21 - base, 22 - circulating piece, 23 - rotating drum, 24 - rotating ring, 25 - through hole, 26 - opening, 27 - connecting frame;

[0028] 51 - flow channel, 52 - pipeline;

[0029] 61 - base, 62 - circulating piece, 63 - rotating drum, 64 - rotating ring.

[0030] The implementation, functional features and advantages of the present application will be further described with reference to the embodiments and the accompanying drawings. DETAILED DESCRIPTION

[0031] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by a person of ordinary skill in the art without creative effort fall within the protection scope of the present application.

[0032] It should be noted that all directional indications, such as up, down, left, right, front, back, etc., in the embodiments of the present application are only used to explain the relative positional relationship, movement condition, etc. between components in a certain posture (as shown in the drawings), and if the certain posture changes, the directional indications also change accordingly.

[0033] In the present application, unless otherwise explicitly specified and limited, the terms “connection”, “fixation” and the like should be understood in a broad sense, for example, “fixation” can be fixed connection, or detachable connection, or integral; can be mechanical connection, or electrical connection; can be direct connection, or indirect connection through an intermediate medium; can be internal connection of two elements or interaction relationship between two elements, unless otherwise explicitly limited. For a person of ordinary skill in the art, the specific meaning of the above terms in the present application can be understood according to the specific circumstances.

[0034] In addition, if the present application has a description of “first”, “second” and the like, the description of “first”, “second” and the like is only for the purpose of description, and cannot be understood as indicating or implying the relative importance of the indicated technical features or implicitly indicating the number of the indicated technical features. Therefore, the features limited by “first”, “second” can explicitly or implicitly include at least one of the features. In addition, the meaning of “and / or” appearing throughout the text includes three parallel schemes. Taking “A and / or B” as an example, it includes A scheme, or B scheme, or A and B schemes. In addition, the technical solutions of each embodiment can be combined with each other, but it must be based on the fact that a person of ordinary skill in the art can realize it, and when the combination of technical solutions appears contradictory or unachievable, it should be considered that the combination of technical solutions does not exist, and is not within the protection scope of the present application.

[0035] Embodiment 1:

[0036] Referring to the drawings Figures 1 to 3 The present embodiment provides a hydrogen energy storage system, the storage system includes a shell 1 and a hydrogen energy supply module, the storage system further includes a storage module 3, a compensation module 4 and a thermal management module 5 coaxially nested in the shell 1 from the inside to the outside;

[0037] The side of the heat management module 5 is provided with a circulation module 2, the inner container of the storage module 3 is provided with a corrugated structure, the compensation module 4 comprises a compensation structure wound on the outer periphery of the corrugated structure, the shell 1 is provided with a first liquid port 11, a second liquid port 12 and a third liquid port 13, and the heat management module 5 is provided with a plurality of flow channels 51 in communication with the first liquid port 11 and the second liquid port 12;

[0038] The circulation module 2 is in communication with a plurality of flow channels 51, and the circulation module 2 comprises a control unit, which manages the heat management path of the storage system by adjusting the opening and closing of the first liquid port 11, the second liquid port 12 and the third liquid port 13. When hydrogen is absorbed, the first liquid port 11 and the third liquid port 13 are opened, and the second liquid port 12 is closed. When hydrogen is released, the first liquid port 11 and the second liquid port 12 are opened, and the third liquid port 13 is closed.

[0039] It should be noted that for the hydrogen energy storage process, if the heat released during the hydrogen absorption stage cannot be timely discharged, it will cause a sudden temperature rise and lead to thermal runaway, which will increase the equilibrium pressure and inhibit the hydrogen absorption reaction. If the heat supply is insufficient during the hydrogen release stage, the system temperature will drop sharply, significantly reducing the desorption rate.

[0040] It should also be noted that the material pulverization caused by repeated hydrogen absorption and release cycles will significantly increase the porosity of the bed body, forming a chain effect of thermal bridge fracture-heat transfer deterioration-reaction lag. Stress concentration caused by powder accumulation may cause the risk of container expansion and cracking. Although the prior art attempts to alleviate the above problems by adding heat-conducting reinforcing phases or improving the heat exchange structure, such as expanded graphite, it often sacrifices the hydrogen storage capacity, and lacks a systematic evaluation method for the overall performance of the device, resulting in a lack of reliable design basis and performance verification means for engineering application.

[0041] Based on the above problems, the hydrogen energy storage system is provided in the embodiment, and the heat during hydrogen absorption and release is dynamically managed through the multi-layer nested heat exchange and the limiting composite structure. The storage structure comprises an inner container with a corrugated structure. When the pressure of the inner container exceeds the threshold value, the compensation metal can undergo a martensitic phase transition to produce a compensation deformation of at least 2%, and cooperate with the axial expansion and contraction of the corrugated structure (maximum compensation amount ± 4mm) to realize dynamic stress compensation.

[0042] It can be understood that the dynamic expansion compensation of the corrugated structure can provide a mechanical basis for the heat management process; and by arranging the circulation module 2 in the shell 1, a suitable heat exchange path is controlled, and it can be understood that the first liquid port 11, the second liquid port 12 and the third liquid port 13 are connected with numerical control valves and communicate with the cooling pipeline through the numerical control valves, and the circulation module 2 and the heat management module 5 form a dynamic cooling / heat storage path in the shell 1. For the cooling path, the first liquid port 11 and the third liquid port 13 are opened, and the second liquid port 12 is closed, at this time, the flow distance of the cooling path in the shell 1 is the shortest, which helps the heat management module 5 to absorb the heat generated in the hydrogen storage process of the storage module 3, and to exchange heat with the external cooling pipeline at the fastest speed to realize the heat management of the hydrogen storage process.

[0043] Similarly, for the heat storage path, the first liquid port 11 and the second liquid port 12 are opened, and the third liquid port 13 is closed, at this time, the flow distance of the heat storage path in the shell 1 is the longest, which helps the heat management module 5 to supplement the heat absorbed by the hydrogen storage process of the storage module 3, and to balance the heat inside the storage module 3 to improve the resolution rate. Not only solves the problem of reaction efficiency fluctuation caused by heat accumulation or insufficient supply of traditional solid-state hydrogen storage devices, but also optimizes the heat exchange efficiency by shortening or lengthening the path length, reduces the energy loss, in addition, the pipeline 52 spirally wound on the outer periphery of the compensation structure further strengthens the contact area of the flow channel 51 and the compensation structure, improves the uniformity and response speed of heat conduction.

[0044] In some embodiments, the maximum compensation amount of the axial expansion is ±4mm.

[0045] In some embodiments, several hydrogen energy storage systems share the same cooling pipeline.

[0046] In the present embodiment, several flow channels 51 include a pipeline 52 spirally wound on the outer periphery of the compensation structure, the openings 26 of the pipeline 52 respectively communicate with the first liquid port 11, the second liquid port 12, and the third liquid port 13 is arranged on one side close to the circulation module 2, and the circulation module 2 is movably arranged in the shell 1.

[0047] In the prior art, the traditional straight pipe flow channel 51 is limited in contact area with the compensation structure, which easily leads to local heat accumulation or uneven heat dissipation, especially in the hydrogen absorption and heat release stage, the heat cannot be quickly exported, which may cause material phase change lag or local overheating. The spiral winding form of the spiral pipeline 52 not only increases the contact area of the flow channel 51 and the compensation structure, but also lengthens the flow distance of the cooling medium through the spiral path, so as to realize more sufficient heat exchange in a limited space. In addition, the turbulent effect induced by the spiral structure can destroy the fluid boundary layer, further enhancing the convective heat transfer coefficient.

[0048] The circulating module 2 is movably arranged in the shell 1, allowing dynamic adjustment of the module position according to the hydrogen absorption / desorption mode, and through displacement, the third liquid port 13 is aligned with the shortest cooling path during hydrogen absorption, and is switched to the heat storage path during hydrogen desorption, further optimizing the layout of the flow channel 51, so that the system can quickly adapt to the change of thermal load under different working conditions, avoiding the energy loss caused by the design redundancy of the traditional fixed flow channel 51. During the hydrogen desorption and heat absorption stage, the movable circulating module 2 can adjust the flow direction of the flow channel 51 to prolong the medium residence time, fully absorb the heat input by the external heat exchanger, and ensure the stability of the hydrogen storage metal resolution rate.

[0049] In the present embodiment, the circulating module 2 comprises a base 21, a circulating part 22 rotatably arranged in the base 21, and a rotating drum 23 arranged inside the circulating part 22. The circulating part 22 is axisymmetric, and the symmetric sides of the circulating part 22 comprise a rotating ring 24 rotatably arranged with the rotating drum 23. The rotating ring 24 is also rotatably arranged in the base 21.

[0050] In order to avoid the vortex or backflow phenomenon caused by the local high pressure or low pressure area of the traditional cooling pipeline, in the present embodiment, the circulating module 2 is arranged to ensure that the fluid enters the flow channel 51 symmetrically from both sides of the circulating module 2, effectively balancing the pressure distribution in the flow channel 51 and avoiding the flow deviation phenomenon. At the same time, the rotating connection of the rotating drum 23 and the rotating ring 24 allows the circulating module 2 to dynamically adjust the opening and closing state of the internal flow channel 51 according to the working condition. Specifically, during the hydrogen absorption stage, the coordinated rotation of the rotating drum 23 and the rotating ring 24 can align the flow channel 51 opening 26 with the shortest cooling path, reducing the flow resistance; and during the hydrogen desorption stage, by adjusting the angle of the rotating drum 23 to prolong the flow channel 51 path, the medium residence time is increased to fully absorb the external heat.

[0051] In the present embodiment, the rotating drum 23 is provided with a plurality of through holes 25, and the side of the rotating ring 24 close to the rotating drum 23 is provided with a plurality of openings 26. The base 21 is provided with a connecting frame 27, and the rotating drum 23 and the rotating ring 24 are movably arranged on the base 21 through the connecting frame 27, and the symmetric sides are connected through the through holes 25 and the openings 26. A plurality of through holes 25 and openings 26 are inclined.

[0052] In the present embodiment, the plurality of through holes 25 distributed at intervals on the rotating drum 23 and the wedge-shaped openings 26 formed on the inner side of the rotating ring 24 are linked through the axial displacement of the connecting frame 27. When the system is switched to the hydrogen absorption mode, the control unit drives the connecting frame 27 to move forward, so that the through holes 25 of the rotating drum 23 and the openings 26 of the rotating ring 24 form an overlapping area. At this time, the cooling medium enters the flow channel 51 symmetrically from both sides of the base 21, the uniformity of flow velocity distribution is improved, and the traditional one-way flow channel 51 is significantly improved.

[0053] The above structure couples mechanical transmission and fluid control, compensates for deformation of the compensation module 4 caused by temperature changes in real time by relative rotation of the rotating ring 24 and the rotating drum 23, and keeps the flow channel 51 of the thermal management module 5 at a constant distance from the outer wall of the compensation module 4, thereby avoiding extrusion of the flow channel 51 caused by thermal expansion and contraction in the traditional structure.

[0054] In some embodiments, the pitch angle of the through hole 25 is 15°, and the inclination angle of the opening 26 is 30°.

[0055] Embodiment 2:

[0056] In this embodiment, the corrugated structure includes a compensation metal for providing expansion compensation capability, and the compensation metal includes 58-63 wt% of Ni, 20-23 wt% of Cr, 8-10 wt% of Mo, and 3.15-4.15 wt% of Nb.

[0057] In some embodiments, the compensation metal includes 58 wt% of Ni, 23 wt% of Cr, 8 wt% of Mo, 3.15 wt% of Nb, 0.2 wt% of Fe, and 0.08 wt% of C, and the balance is the total amount of impurities that can exist.

[0058] The melting process adopted is vacuum induction melting and electroslag remelting, the melting temperature is 1580℃, and after 1.5h of solid solution treatment at 1050℃, water quenching is performed, and then aging treatment is performed at 620℃ for 8h.

[0059] In this embodiment, a dense oxide film is formed by a high Cr content, which significantly reduces the hydrogen permeation rate, and is suitable for low-temperature hydrogen absorption scenarios. The optimization of the thermal expansion coefficient makes the axial compensation amount of the corrugated structure reach ±3mm. In industrial application, the compensation metal in this embodiment is matched with surface nitriding treatment to further improve the hydrogen embrittlement resistance.

[0060] Embodiment 3:

[0061] In some embodiments, the compensation metal includes 60.5 wt% of Ni, 21.5 wt% of Cr, 9 wt% of Mo, 3.65 wt% of Nb, and 0.03 wt% of O, and the balance is the total amount of impurities that can exist.

[0062] The melting process adopted is plasma arc melting, the melting temperature is 1620℃, and after 2h of solid solution treatment at 1100℃, cold rolling deformation of 15% is performed, and then aging treatment is performed at 550℃ for 10h.

[0063] Embodiment 4:

[0064] In some embodiments, the compensation metal includes 63 wt% of Ni, 20 wt% of Cr, 10 wt% of Mo, 4.15 wt% of Nb, and 0.05 wt% of N, and the balance is the total amount of impurities that can exist.

[0065] The smelting process adopted is plasma arc smelting, and the smelting temperature is 1720℃; after 1150℃ solid solution treatment for 3h, twice aging (750℃×4h+600℃×12h) is performed.

[0066] According to the data comparison table below,

[0067] Performance index Prior art Example 2 Example 3 Example 4 Coefficient of thermal expansion 13.1 x 10⁻ 6 / K]] 9.2 x 10⁻ 6 / K]] 8.7 x 10⁻ 6 / K]] 8.1 x 10⁻ 6 / K]] Yield strength 380 MPa 420 MPa 455 MPa 480 MPa Hydrogen permeation rate 2.2 x 10⁻¹ 0 ]] 5.2 x 10⁻¹ 0 ]] 4.8 x 10⁻¹ 0 ]] 4.5 x 10⁻¹ 0 ]] Cyclic life 8600 times 10,500 times 15,200 times 18,000 times High temperature strength MPa 320 MPa 485 MPa 620 MPa Hydrogen embrittlement threshold 25 MPa·m 0 . 5 ]]> 28 MPa·m 0 . 5 ]]> 34 MPa.m 0 . 5 ]]> 38 MPa.m 0 . 5 ]]> Manufacturing cost 100% 95% 112% 124%

[0068] In combination with the above table, in terms of the coefficient of thermal expansion, the values of examples 2-4 are significantly reduced compared with the prior art, and the thermal stability of the material is significantly improved. This improvement effectively solves the problem of thermal stress accumulation of the hydrogen storage system caused by hydrogen absorption and desorption cycles. The yield strength is increased by 10%-26%, which proves that the material deformation resistance and structural reliability are enhanced. The hydrogen embrittlement threshold KTH is increased by 12%-52%, which shows a breakthrough improvement in hydrogen embrittlement resistance, and directly verifies the improvement effect of the technical scheme on the durability of the device.

[0069] Example 5:

[0070] In this embodiment, a hydrogen storage metal for hydrogen storage is arranged in the storage module, and the hydrogen storage metal is composed of awt% Ti a Mn b Cr c V d Zr e Fe f , Bwt% La x Ni y and Cwt% V, wherein a, b, c, d, e, f, x and y are molar ratios; 0.75≤a≤0.92; 1.3≤b≤1.8; 0.3≤c≤0.6; 0.15≤d≤0.4; 0.05≤e≤0.2; 0.01≤f≤0.1; 75≤A≤90; 5≤B≤15; 3≤C≤10; 0.95≤x≤1.05; 4.85≤y≤5.15.

[0071] It can be understood that, through specific hydrogen storage metal component design and multi-element synergistic optimization, the problems of pulverization, heat conduction performance degradation and reaction kinetics lag caused by lattice volume expansion / contraction in the hydrogen absorption and desorption cycle of traditional solid-state hydrogen storage alloys are solved.

[0072] The specific technical means include:

[0073] Titanium-based alloy is used as the core to build a high-toughness matrix, and by limiting the molar ratio range of Ti, Mn, Cr, V, Zr and Fe, the lattice constant and hydrogen atom occupation energy are controlled at the atomic scale. Among them, the high hydrogen absorption capacity of Ti and the lattice distortion inhibition capacity of Zr are combined, so that the volume expansion rate of the alloy when absorbing hydrogen is reduced from 24% of the conventional LaNi5 alloy to 8.5%, and the synergistic solid solution strengthening effect of Cr and V is formed, forming a dual-phase structure with nanoscale precipitates, which significantly improves the anti-powdering capacity.

[0074] Rare earth elements are introduced as catalytic phases, and their unique 4f electron orbits form weak chemical bonds with hydrogen atoms, reducing the hydrogen dissociation activation energy from 0.45 eV of conventional alloys to 0.28 eV, which significantly shortens the hydrogen absorption induction period.

[0075] By adding 3-10wt% of free vanadium, a vanadium-rich passivation layer is formed on the surface of the alloy, which inhibits the hydrogen permeation-induced grain boundary embrittlement, and at the same time, matches the thermal expansion coefficient with the compensation metal in the thermal management module to avoid interface thermal stress concentration, significantly improving the pressure stability of the hydrogen absorption and desorption process.

[0076] In the present embodiment, the hydrogen storage metal composition satisfies:

[0077] a+e=0.8-1.05;

[0078] b+c+d=1.8-2.2.

[0079] In some embodiments, the hydrogen storage metal includes:

[0080] 75wt% of Ti 0.75 Mn 1.3 Cr 0.3 V 0.2 Zr 0.05 Fe 0.01 ;

[0081] 5wt% of La 0.95 Ni 4.85 ;

[0082] 3wt% of V;

[0083] Embodiment 6:

[0084] In some embodiments, the hydrogen storage metal includes:

[0085] 82.5wt% of Ti 0.835 Mn 1.55 Cr 0.45 V 0.27 5Zr 0.125 Fe 0.055 ;

[0086] 10wt% of LaNi5;

[0087] 6.5wt% of V.

[0088] Example 7:

[0089] In some embodiments, the hydrogen storage metal comprises:

[0090] 90wt% of Ti 0.92 Mn 1.6 Cr 0.6 V 0.4 Z r0.13 Fe 0.1 ;

[0091] 15wt% of La 1.05 Ni 5.15 ;

[0092] 10wt% of V.

[0093] In combination of Examples 5 to 7, the following table of data comparison is obtained,

[0094] Performance index Prior art Example 5 Example 6 Example 7 Coefficient of thermal expansion 13.1 9.8 8.9 8.3 Yield strength (MPa) 380 410 470 490 Hydrogen permeability (x 10⁻¹ 0 mol m⁻¹ s⁻¹) 2.2 5.8 4.5 4 Cyclic life (times) 8600 10200 15800 17500 High temperature strength (200°C, MPa) 320 380 510 600 hydrogen embrittlement threshold KTH (MPa·m 0 . 5 )]]> 25 27 35 39 Hydrogen storage density (wt%) 1.4 2 2.3 2.4 Hydrogen absorption rate (g / s·m³) 0.12 0.28 0.39 0.42 Manufacturing cost (relative value) 1 0.97 1.15 1.3

[0095] In combination of the above table, in terms of thermodynamic stability, due to the accurate control of the molar ratio of titanium to zirconium, the high hydrogen absorption capacity of titanium and the lattice distortion inhibition ability of zirconium synergistically work together to disperse the lattice stress generated during the hydrogen absorption expansion stage to the nanoscale precipitated phase, combined with the solid solution strengthening effect of chromium and vanadium, the volume expansion rate is compressed from 24% of the prior art to 7.8% to 9.2%, thereby significantly reducing the heat exchange load of the thermal management module.

[0096] In terms of anti-pulverization ability, its nanobiphasic structure inhibits crack propagation through dislocation pinning effect, while the vanadium-rich passivation layer formed by free-state vanadium at the grain boundary effectively reduces hydrogen permeability and blocks the hydrogen-induced embrittlement path.

[0097] In terms of reaction kinetics, the weak bonding effect of the electron orbit of the lanthanum-nickel catalytic phase with hydrogen atoms greatly reduces the hydrogen dissociation activation energy, and the high surface activity of titanium significantly reduces the hydrogen adsorption energy, thereby shortening the hydrogen absorption induction period to 8 seconds. In terms of safety, the flow accumulation of the alloy powder is inhibited by the axial constraint of the carbon fiber, so that the powder bulk density after cycling is improved, the thermal conductivity coefficient is significantly improved, and the local temperature difference is reduced from 45 degrees Celsius to 6 degrees Celsius. The overall data verifies the strong correlation between the component parameters and the performance indicators, and the technical scheme solves the problems of pulverization, thermal conductivity degradation and reaction lag of traditional hydrogen storage alloys through multi-element synergistic optimization, while expanding the economic performance and performance adaptation range of the application scenario.

[0098] Example 8:

[0099] In this embodiment, the compensating structure comprises 60-65wt% carbon fibres and 35-40wt% epoxy resin matrix.

[0100] In some embodiments, the compensating structure comprises:

[0101] 80wt% Ti 0.8 Mn 1.5 Cr 0.4 V 0.3 Fe 0.05 ;

[0102] 10wt% LaNi5;

[0103] 10wt% V

[0104] In some embodiments, the compensating structure comprises:

[0105] 85wt% Ti 0.925 Mn 1.6 Cr 0.35 V 0.25 Zr 0.125 Fe 0.08 ;

[0106] 8wt% La 1.02 Ni 5.05 ;

[0107] 7wt% V;

[0108] In some embodiments,

[0109] In some embodiments, the compensating structure comprises:

[0110] 90wt% Ti 1.05 Mn 1.3 Cr 0.5 V 0.4 Fe 0.1 ;

[0111] 5wt% La0.95Ni4.85;

[0112] 5wt% V.

[0113] It can be understood that, in order to solve the problems of high volume expansion rate, serious cycle pulverization and slow hydrogen diffusion kinetics caused by uncontrollable lattice distortion of traditional titanium-based hydrogen storage materials, the high hydrogen storage capacity of titanium is used as a basis, and the zirconium element is introduced to inhibit the lattice distortion. When the total titanium-zirconium molar ratio is less than 0.8, the insufficient titanium content causes the hydrogen storage capacity to decrease to 1.8wt%, and the lattice expansion rate is as high as 12%; when it exceeds 1.05, the excessive titanium causes the abnormal increase of the lattice constant, and the pulverization rate increases to 28% after cycling. Titanium main lattice carries hydrogen atoms, and zirconium disperses stress through local distortion, so that the volume expansion rate is reduced from 24% of the traditional alloy to 6.5%, and the hydrogen storage density is stabilized at 2.3wt%. Secondly, the addition of zirconium induces the formation of nanoscale zirconia precipitates, and the high hardness and low hydrogen solubility of zirconia inhibit crack propagation. For example, in the embodiment, when the titanium-zirconium molar ratio is 1.05, the cycle life is increased to 16,500 times, which is increased by 175% compared with the unbalanced ratio scheme. Finally, zirconium forms a zirconium-rich layer on the surface of the alloy, reduces the hydrogen adsorption potential barrier, increases the hydrogen diffusion coefficient, and increases the hydrogen absorption rate by 2.7 times, and shortens the induction period to 8 seconds.

[0114] Embodiment 9:

[0115] In this embodiment, the storage system includes a heat exchanger thermally coupled to the heat management path. The heat exchanger and the through hole 25 of the rotating drum 23 of the circulation module 2 form a turbulent effect due to the inclined design, and through the linkage displacement of the opening 26 of the rotating ring 24 and the connecting frame 27 of the base 21, the spacing change of the flow channel 51 caused by the deformation of the compensation module 4 is compensated in real time, which helps to maintain the constant contact pressure between the wall surface of the flow channel 51 and the compensation structure.

[0116] The above is only the preferred embodiment of the present application, and does not limit the patent scope of the present application, and any equivalent structure or equivalent process transformation using the content of the specification and drawings of the present application, or direct or indirect application in other related technical fields, are also included in the patent protection scope of the present application.

Claims

1. A hydrogen energy storage system, the storage system comprising a housing and a hydrogen energy supply module, characterized by, The storage system further comprises a storage module, a compensation module and a thermal management module coaxially nested in the shell from inside to outside; The side of the thermal management module is provided with a circulation module, the inner container of the storage module is provided with a corrugated structure, the compensation module comprises a compensation structure wound on the outer periphery of the corrugated structure, the shell is provided with a first liquid port, a second liquid port and a third liquid port, and the thermal management module is provided with a plurality of flow channels in communication with the first liquid port and the second liquid port; The circulation module is in communication with a plurality of flow channels, and the circulation module comprises a control unit, which manages the thermal management path of the storage system by adjusting the opening and closing of the first liquid port, the second liquid port and the third liquid port. When hydrogen is absorbed, the first liquid port and the third liquid port are opened, and the second liquid port is closed. When hydrogen is released, the first liquid port and the second liquid port are opened, and the third liquid port is closed. The storage module is internally provided with hydrogen storage metal for hydrogen storage, and the hydrogen storage metal is composed of Awt% Ti a Mn b Cr c V d Zr e Fe f , Bwt% La x Ni y and Cwt% V, wherein a, b, c, d, e, f, x and y are molar ratios; 0.75≤a≤0.92; 1.3≤b≤1.8; 0.3≤c≤0.6; 0.15≤d≤0.4; 0.05≤e≤0.2; 0.01≤f≤0.1; 75≤A≤90; 5≤B≤15; 3≤C≤10; 0.95≤x≤1.05; 4.85≤y≤5.15; The compensation structure comprises 60-65wt% carbon fibers and 35-40wt% epoxy resin matrix; The hydrogen storage metal composition satisfies: a+e=0.8~1.05; b+c+d=1.8~2.

2.

2. A hydrogen energy storage system as claimed in claim 1, wherein, A plurality of flow channels include a pipe spirally wound on the outer periphery of the compensation structure, the openings of the pipe are in communication with the first liquid port and the second liquid port, respectively, and the third liquid port is arranged on the side close to the circulation module. The circulation module is movably arranged in the shell.

3. A hydrogen energy storage system as in claim 1, wherein, The circulation module comprises a base, a circulating member rotatably arranged in the base, and a rotating drum arranged inside the circulating member. The circulating member is an axisymmetric structure, and the symmetric sides of the circulating member comprise a rotating ring rotatably arranged with the rotating drum. The rotating ring is also rotatably arranged in the base.

4. A hydrogen energy storage system as claimed in claim 3, wherein, The rotating drum is provided with a plurality of through holes, and the side of the rotating ring close to the rotating drum is provided with a plurality of openings. The base is provided with a connecting frame. The rotating drum and the rotating ring are movably arranged on the base through the connecting frame and are in communication on the symmetric sides through the through holes and the openings.

5. A hydrogen energy storage system as claimed in claim 4, wherein, A plurality of through holes and openings are inclined.

6. A hydrogen energy storage system as in claim 1, wherein, The corrugated structure comprises a compensation metal for providing expansion compensation capability. The compensation metal comprises 58-63wt% Ni, 20-23wt% Cr, 8-10wt% Mo and 3.15-4.15wt% Nb.

7. A hydrogen energy storage system as in claim 1, wherein, The storage system comprises a heat exchanger thermally coupled to the thermal management path.

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