Hydrogen energy storage system

Abstract

The invention relates to the technical field of hydrogen energy storage equipment, in particular to 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 heat management module which are coaxially nested in the shell from inside to outside. A circulation module is arranged on the side edge of the heat management module, a corrugated structure is arranged on an inner container of the storage module, dynamic heat management is carried out on heat during hydrogen absorption / hydrogen desorption through a multi-layer nested heat exchange and limiting composite structure, and a proper heat exchange path is controlled by arranging the circulation module in the shell. The problem of reaction efficiency fluctuation caused by heat accumulation or insufficient supply of a traditional solid hydrogen storage device is solved, the heat exchange efficiency is optimized by shortening or prolonging the path length, and the energy loss is reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrogen energy storage devices, and specifically refers to a hydrogen energy storage system. Background Art

[0002] As the clean secondary energy with the most development potential in the 21st century, hydrogen energy has become an important direction for global energy transformation by virtue of its advantages such as high combustion calorific value, wide sources, and diverse utilization forms.

[0003] However, the low-density characteristic of hydrogen leads to significant technical bottlenecks in its storage and transportation links, severely restricting the industrial application process. Currently, the mainstream hydrogen storage technologies include high-pressure gaseous hydrogen storage, cryogenic liquid hydrogen storage, and solid material hydrogen storage. Taking the solid material hydrogen storage device as an example, the pulverization phenomenon caused by the lattice volume change during the hydrogen absorption and desorption process of the existing hydrogen storage alloy, as well as the resulting deterioration of the bed thermal conductivity and stress concentration problems, have become important factors 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 hydrogen storage device: the dynamic thermal management requirements of heat release during hydrogen absorption and heat absorption during hydrogen desorption, the mass transfer resistance between the hydrogen gas flow field and the porous medium, and the flow and accumulation of alloy powder due to volume effects are intertwined, forming a vicious cycle. Summary of the Invention

[0005] The main purpose of the present invention is to provide a hydrogen energy storage system, aiming to solve the problem that the existing solid hydrogen storage device cannot meet the dynamic thermal management requirements of heat during hydrogen absorption / desorption.

[0006] To achieve the above object, the present invention provides a hydrogen energy storage system, which includes a housing and a hydrogen energy supply module. The storage system further includes a storage module, a compensation module, and a thermal management module that are coaxially nested inside the housing from inside to outside;

[0007] A circulation module is arranged on the side of the thermal management module. The inner tank of the storage module is provided with a corrugated structure. The compensation module includes a compensation structure wound around the outer periphery of the corrugated structure. The housing is provided with a first liquid port, a second liquid port, and a third liquid port. A number of flow channels communicating with the first liquid port and the second liquid port are arranged in the thermal management module;

[0008] The circulation module is communicated with a number of the flow channels. The circulation module includes 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. During hydrogen absorption, the first liquid port and the third liquid port are opened, and the second liquid port is closed. During hydrogen desorption, the first liquid port and the second liquid port are opened, and the third liquid port is closed.

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

[0010] Optionally, the circulation module includes a base, a circulation member rotatably arranged in the base, and a rotating cylinder arranged inside the circulation member. The circulation member is an axisymmetric structure. The symmetric side of the circulation member includes a rotating ring rotatably arranged with the rotating cylinder, and the rotating ring is also rotatably arranged in the base.

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

[0012] Optionally, several of the through holes and the openings are inclinedly arranged.

[0013] Optionally, the corrugated structure includes a compensating metal for providing telescopic compensation ability. The compensating 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.

[0014] Optionally, a hydrogen storage metal for hydrogen storage is configured in the storage module. The hydrogen storage metal consists of A wt.% of Ti a Mn b Cr c V d Zr e Fe f and B wt.% of La x Ni y and C wt.% of V, where 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 60-65 wt% of carbon fiber and 35-40 wt% of 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 to 2.2.

[0019] Optionally, the storage system includes a heat exchanger thermally connected to the heat management path.

[0020] A hydrogen energy storage system proposed in an embodiment of the present invention performs dynamic thermal management on the heat during hydrogen absorption / hydrogen release through a multi-layer nested heat exchange and limit composite structure, and also controls a suitable heat exchange path by setting a circulation module in the housing. It can be understood that the first liquid port, the second liquid port, and the third liquid port are all connected with numerical control valves and communicated with the cooling pipeline through the numerical control valves. The circulation module and the heat management module form a dynamic cooling / heat storage path in the housing. 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 housing is the shortest, which helps the heat management module absorb the heat generated during the hydrogen absorption process of the storage module and exchange heat with the external cooling pipeline at the fastest speed, realizing the thermal management during the hydrogen absorption process; it not only solves the problem of reaction efficiency fluctuation caused by heat accumulation or insufficient supply in traditional solid hydrogen storage devices, but also optimizes the heat exchange efficiency by shortening or lengthening the path length, reducing energy loss. In addition, the pipeline design spirally wound around the outer periphery of the compensation structure further strengthens the contact area between the flow channel and the compensation structure, improving the uniformity and response speed of heat conduction. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0022] Figure 2 is a schematic internal structure diagram of the system of the present invention;

[0023] Figure 3 is a schematic internal structure diagram of the circulation module of the present invention.

[0024] Reference Signs:

[0025] 1 - housing, 2 - circulation module, 3 - storage module, 4 - compensation module, 5 - heat management module;

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

[0027] 21 - base, 22 - circulation part, 23 - rotating cylinder, 24 - rotating ring, 25 - through hole, 26 - opening, 27 - connecting frame;

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

[0029] 61 - base, 62 - circulation part, 63 - rotating cylinder, 64 - rotating ring.

[0030] The realization, functional features and advantages of the present invention will be further described with reference to the embodiments and the accompanying drawings. Detailed implementation manners

[0031] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts shall fall within the protection scope of the present invention.

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

[0033] In the present invention, unless otherwise clearly defined and limited, the terms "connection", "fixation", etc. shall be understood in a broad sense. For example, "fixation" may be a fixed connection, a detachable connection, or integrated; it may be a mechanical connection or an electrical connection; it may be directly connected or indirectly connected through an intermediate medium, and it may be the internal connection of two components or the interaction relationship between two components, unless otherwise clearly limited. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific situations.

[0034] In addition, if there are descriptions involving "first", "second", etc. in the embodiments of the present invention, such descriptions of "first", "second", etc. are only for descriptive purposes and cannot be understood as indicating or implying their relative importance or implicitly indicating the quantity of the indicated technical features. Thus, the features defined with "first" and "second" may explicitly or implicitly include at least one of such features. In addition, the meaning of "and / or" appearing throughout the text includes three parallel solutions. Taking "A and / or B" as an example, it includes solution A, solution B, or a solution where A and B are satisfied simultaneously. In addition, the technical solutions between the various embodiments can be combined with each other, but it must be based on the fact that those of ordinary skill in the art can implement them. When the combination of technical solutions is contradictory or cannot be implemented, it should be considered that such a combination of technical solutions does not exist and is not within the protection scope required by the present invention.

[0035] Embodiment 1:

[0036] Refer to the attached Figures 1 to 3, this embodiment provides a hydrogen energy storage system, the storage system includes a shell 1 and a hydrogen energy supply module, the storage system also includes a storage module 3, a compensation module 4 and a thermal management module 5 coaxially nested in the shell 1 from inside to outside;

[0037] The side of the thermal management module 5 is provided with a circulation module 2, the inner tank of the storage module 3 is provided with a corrugated structure, the compensation module 4 includes a compensation structure wound around 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 thermal management module 5 is provided with a plurality of flow channels 51 connected with the first liquid port 11 and the second liquid port 12;

[0038] The circulation module 2 is connected to the plurality of flow channels 51, and the circulation module 2 includes a control unit, which manages the thermal 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 absorbing hydrogen, the first liquid port 11 and the third liquid port 13 are opened, and the second liquid port 12 is closed. When releasing hydrogen, 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 storage process of hydrogen energy, if the heat released during the hydrogen absorption stage cannot be discharged in time, it will cause a sudden rise in local temperature and trigger thermal runaway, causing the equilibrium pressure to increase 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 decomposition rate.

[0040] It should also be noted that the material pulverization caused by repeated hydrogen absorption and desorption cycles will significantly increase the porosity of the bed, forming a chain effect of thermal bridge rupture-heat transfer deterioration-reaction lag. At the same time, the stress concentration caused by powder accumulation may cause the risk of container rupture. Although the existing technology attempts to alleviate the above problems by adding thermal conductivity enhancement phases or improving heat exchange structures, such as expanded graphite, it often sacrifices 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 methods for engineering applications.

[0041] Based on the above problems, a hydrogen energy storage system is provided in the present embodiment, and dynamic thermal management of the heat during hydrogen absorption / desorption is performed through a multi-layer nested heat exchange and limiting composite structure. The storage structure includes an inner liner with a corrugated structure. When the pressure in the inner liner exceeds a threshold value, the compensation metal can undergo a martensitic phase transformation to produce at least 2% compensatory deformation, and cooperate with the axial expansion and contraction of the corrugated structure (maximum compensation amount ±4mm) to achieve dynamic stress compensation.

[0042] It can be understood that the dynamic telescopic compensation of the corrugated structure provides a mechanical basis for the heat management process; a circulation module 2 is arranged in the housing 1 to control a suitable heat exchange path. It can also be understood that the first liquid port 11, the second liquid port 12, and the third liquid port 13 are all connected with numerical control valves and communicated with the cooling pipeline through the numerical control valves. The circulation module 2 and the heat management module 5 form a dynamic cooling / heat storage path in the housing 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 housing 1 is the shortest, which helps the heat management module 5 absorb the heat generated during the hydrogen absorption process of the storage module 3 and exchange heat with the external cooling pipeline at the fastest speed, realizing the heat management during the hydrogen absorption 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 housing 1 is the longest, which helps the heat management module 5 supplement the heat absorbed during the hydrogen release process of the storage module 3 and balance the heat inside the storage module 3 to improve the desorption rate. It not only solves the problem of reaction efficiency fluctuation caused by heat accumulation or insufficient heat supply in the traditional solid-state hydrogen storage device, but also optimizes the heat exchange efficiency by shortening or lengthening the path length, reducing the energy loss. In addition, the design of the pipeline 52 spirally wound around the outer periphery of the compensation structure further strengthens the contact area between the flow channel 51 and the compensation structure, improving the uniformity and response speed of heat conduction.

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

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

[0046] In this embodiment, several of the flow channels 51 include a pipeline 52 spirally wound around the outer periphery of the compensation structure. The openings 26 of the pipeline 52 are respectively communicated with the first liquid port 11 and the second liquid port 12. 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 housing 1.

[0047] In the prior art, due to the limited contact area between the traditional straight pipe type flow channel 51 and the compensation structure, local heat accumulation or uneven heat dissipation is likely to occur. 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 between the flow channel 51 and the compensation structure, but also extends the flow distance of the cooling medium through the spiral path, so as to achieve more sufficient heat exchange in a limited space. In addition, the turbulent flow effect induced by the spiral structure can break the fluid boundary layer and further enhance the convective heat transfer coefficient.

[0048] The circulation module 2 is disposed within the housing 1 and allows for dynamic adjustment of the module position according to the hydrogen absorption / hydrogen release mode. During hydrogen absorption, the third liquid port 13 is aligned with the shortest cooling path through displacement, and during hydrogen release, it switches to the heat storage path, further optimizing the layout of the flow channel 51, enabling the system to quickly adapt to heat load changes under different working conditions and avoiding energy losses caused by design redundancy in traditional fixed flow channels 51. During the endothermic stage of hydrogen release, the movable circulation module 2 can adjust the flow direction of the flow channel 51 to extend the residence time of the medium, fully absorb the heat input by the external heat exchanger, and ensure the stability of the desorption rate of the hydrogen storage metal.

[0049] In this embodiment, the circulation module 2 includes a base 21, a circulation member 22 rotatably disposed within the base 21, and a rotating cylinder 23 disposed inside the circulation member 22. The circulation member 22 has an axisymmetric structure, and the symmetric side of the circulation member 22 includes a rotating ring 24 rotatably disposed with the rotating cylinder 23, and the rotating ring 24 is also rotatably disposed within the base 21.

[0050] To avoid vortex or backflow phenomena caused by local high-pressure or low-pressure areas in traditional cooling pipelines, in this embodiment, by setting the circulation module 2, it is ensured that the fluid enters the flow channel 51 symmetrically from both sides of the circulation module 2, effectively balancing the pressure distribution within the flow channel 51 and avoiding the phenomenon of uneven flow. At the same time, the rotational connection between the rotating cylinder 23 and the rotating ring 24 allows the circulation module 2 to dynamically adjust the opening and closing state of the internal flow channel 51 according to the working conditions. Specifically, during the hydrogen absorption stage, the coordinated rotation of the rotating cylinder 23 and the rotating ring 24 can align the opening 26 of the flow channel 51 with the shortest cooling path, reducing the flow resistance; while during the hydrogen release stage, by adjusting the angle of the rotating cylinder 23, the path of the flow channel 51 is extended, increasing the residence time of the medium to fully absorb external heat.

[0051] In this embodiment, a plurality of through holes 25 are provided on the rotating cylinder 23, a plurality of openings 26 are provided on the side of the rotating ring 24 close to the rotating cylinder 23, and a connecting frame 27 is provided within the base 21. The rotating cylinder 23 and the rotating ring 24 are movably disposed on the base 21 through the connecting frame 27 and are connected symmetrically through the through holes 25 and the openings 26. A plurality of the through holes 25 and the openings 26 are all inclined.

[0052] In this embodiment, a plurality of through holes 25 spaced apart on the rotating cylinder 23 are linked with the wedge-shaped openings 26 formed on the inner side of the rotating ring 24 through the axial displacement of the connecting frame 27. When the system switches to the hydrogen absorption mode, the control unit drives the connecting frame 27 to move forward, causing the overlapping area to form between the through holes 25 of the rotating cylinder 23 and the openings 26 of the rotating ring 24. At this time, the cooling medium enters the flow channel 51 symmetrically from both sides of the base 21, and the uniformity of the flow velocity distribution is improved, showing a significant improvement compared to the traditional unidirectional flow channel 51.

[0053] The above structure couples mechanical transmission and fluid control, and uses the relative rotation of the rotating ring 24 - rotating cylinder 23 to compensate in real time for the deformation of the compensation module 4 caused by temperature changes, so that the flow channel 51 of the thermal management module 5 always maintains a constant distance from the outer wall of the compensation module 4, avoiding the extrusion of the flow channel 51 caused by thermal expansion and contraction in the traditional structure.

[0054] In some embodiments, the spacing angle of the through holes 25 is 15°; the inclination angle of the openings 26 is 30°.

[0055] Embodiment 2:

[0056] In this embodiment, the corrugated structure includes a compensation metal for providing telescopic compensation ability, 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 possible impurities.

[0058] The melting process adopted is vacuum induction melting and electroslag remelting, with a melting temperature of 1580°C; solution treatment at 1050°C for 1.5 h followed by water quenching, and then aging treatment at 620°C for 8 h.

[0059] In this embodiment, a dense oxide film is formed by a high Cr content, significantly reducing the hydrogen permeability, being suitable for low-temperature hydrogen absorption scenarios, and the optimization of the thermal expansion coefficient enables the axial compensation amount of the corrugated structure to reach ±3 mm. During industrial application, the compensation metal in this embodiment is combined with surface nitriding treatment to further enhance 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 possible impurities.

[0062] The melting process adopted is plasma arc melting, with a melting temperature of 1620°C; solution treatment at 1100°C for 2 h followed by cold rolling with a deformation amount of 15% and then aging treatment at 550°C for 10 h.

[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 possible impurities.

[0065] The melting process adopted is plasma arc melting, and the melting temperature is 1720 °C; after solution treatment at 1150 °C for 3 h, two aging treatments are carried out (750 °C × 4 h + 600 °C × 12 h).

[0066] Combining Examples 2 to 4, the following data comparison table is obtained.

[0067]

[0068]

[0069] Combined with the above table, in terms of the coefficient of thermal expansion, the values of Examples 2 - 4 are significantly lower than those of the prior art, significantly improving the thermal stability of the material. This improvement effectively solves the problem of thermal stress accumulation in the hydrogen storage system caused by the hydrogen absorption and desorption cycle; the yield strength is increased by 10% - 26%, proving that the anti - deformation ability and structural reliability of the material are enhanced; the hydrogen embrittlement threshold KTH is increased by 12% - 52%, showing a breakthrough improvement in the anti - hydrogen embrittlement performance, directly verifying the improvement effect of the technical solution on the durability of the device.

[0070] Example 5:

[0071] In this example, a hydrogen storage metal for hydrogen storage is configured in the storage module, and the hydrogen storage metal is composed of Ti of Awt.%, a Mn b Cr c V d Zr e Fe f , La of Bwt.%, x Ni y and V of Cwt.%, where 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.

[0072] It can be understood that through the design of specific hydrogen storage metal components and the collaborative optimization of multiple elements, the problems of pulverization, deterioration of thermal conductivity, and reaction kinetic retardation caused by lattice volume expansion / contraction during the hydrogen absorption and desorption cycle of traditional solid - state hydrogen storage alloys are solved.

[0073] Specific technical means include:

[0074] Construct a high-toughness matrix with a titanium-based alloy as the core. By limiting the molar ratio ranges of Ti, Mn, Cr, V, Zr, and Fe, the lattice constant and the hydrogen atom site occupancy energy are regulated at the atomic scale. Among them, the combination of the high hydrogen absorption capacity of Ti and the lattice distortion inhibition ability of Zr reduces the volume expansion rate of the alloy during hydrogen absorption from 24% of the conventional LaNi5 alloy to 8.5%. Combined with the synergistic solid solution strengthening effect of Cr and V, a duplex structure with nanoscale precipitation phases is formed, significantly enhancing the anti-pulverization ability.

[0075] Introduce rare earth elements as the catalytic phase. Their unique 4f electron orbitals form weak chemical bonds with hydrogen atoms, reducing the hydrogen dissociation activation energy from 0.45 eV of the conventional alloy to 0.28 eV, and breakthroughly shortening the hydrogen absorption induction period.

[0076] By adding 3-10 wt% of free vanadium, a vanadium-rich passivation layer is constructed on the alloy surface to inhibit the grain boundary embrittlement caused by hydrogen permeation. At the same time, it forms a thermal expansion coefficient match with the compensation metal in the thermal management module to avoid interface thermal stress concentration, significantly improving the pressure stability during the hydrogen absorption and desorption process.

[0077] In this embodiment, the hydrogen storage metal composition satisfies:

[0078] a + e = 0.8 - 1.05;

[0079] b + c + d = 1.8 - 2.2.

[0080] In some embodiments, the hydrogen storage metal includes:

[0081] 75 wt% of Ti 0.75 Mn 1.3 Cr 0.3 V 0.2 Zr 0.05 Fe 0.01 ;

[0082] 5 wt% of La 0.95 Ni 4.85 ;

[0083] 3 wt% of V;

[0084] Example 6:

[0085] In some embodiments, the hydrogen storage metal includes:

[0086] 82.5 wt% of Ti 0.835 Mn 1.55 Cr 0.45 V 0.27 5Zr 0.125 Fe 0.055 ;

[0087] 10 wt% of LaNi5;

[0088] 6.5 wt% of V.

[0089] Example 7:

[0090] In some embodiments, the hydrogen storage metal comprises:

[0091] 90 wt% of Ti 0.92 Mn 1.6 Cr 0.6 V 0.4 Z r0.13 Fe 0.1 ;

[0092] 15 wt% of La 1.05 Ni 5.15 ;

[0093] 10 wt% of V.

[0094] Combining Examples 5 to 7, the following data comparison table is obtained.

[0095]

[0096] Combined with the above table, in terms of thermodynamic stability, due to the precise control of the molar ratio of titanium to zirconium, the synergistic effect of the high hydrogen absorption capacity of titanium and the ability of zirconium to inhibit lattice distortion disperses the lattice stress generated during the hydrogen absorption expansion stage to the nanoscale precipitation phase. Combining the solid solution strengthening effects of chromium and vanadium, the volume expansion rate is compressed from 24% in the prior art to 7.8% to 9.2%, thus significantly reducing the heat exchange load of the thermal management module.

[0097] In terms of anti-pulverization ability, its nano-dual-phase structure inhibits crack propagation through the dislocation pinning effect. At the same time, the vanadium-rich passivation layer formed by free vanadium at the grain boundaries effectively reduces the hydrogen permeability and blocks the hydrogen embrittlement path.

[0098] At the reaction kinetics level, the weak bonding interaction between the electron orbit of the lanthanum-nickel catalytic phase and the hydrogen atom significantly reduces the hydrogen dissociation activation energy, and the high surface activity of titanium significantly decreases the hydrogen adsorption energy, thus shortening the hydrogen absorption induction period to 8 seconds. In terms of safety, the axial constraint of carbon fiber inhibits the flow and accumulation of alloy powder, increasing the powder packing density after cycling and significantly improving the thermal conductivity, and reducing the local temperature difference from 45 degrees Celsius to 6 degrees Celsius. The overall data verifies the strong correlation between the component parameters and the performance indicators. The technical solution solves the problems of pulverization, poor thermal conductivity, and reaction hysteresis of traditional hydrogen storage alloys through multi-element synergistic optimization, while expanding the economic and performance adaptation range of the application scenarios.

[0099] Example 8:

[0100] In this embodiment, the compensation structure comprises 60-65 wt% carbon fiber and 35-40 wt% epoxy resin matrix.

[0101] In some embodiments, the compensation structure comprises:

[0102] 80 wt% of Ti 0.8 Mn 1.5 Cr 0.4 V 0.3 Fe 0.05 ;

[0103] 10 wt% of LaNi5;

[0104] 10 wt% of V

[0105] In some embodiments, the compensation structure comprises:

[0106] 85 wt% of Ti 0.925 Mn 1.6 Cr 0.35 V 0.25 Zr 0.125 Fe 0.08 ;

[0107] 8 wt% of La 1.02 Ni 5.05 ;

[0108] 7 wt% of V;

[0109] In some embodiments,

[0110] In some embodiments, the compensation structure comprises:

[0111] 90 wt% of Ti 1.05 Mn 1.3 Cr 0.5 V 0.4 Fe 0.1 ;

[0112] 5 wt% of La0.95Ni4.85;

[0113] 5 wt% of V.

[0114] It is understandable that, in view of the problems of traditional titanium-based hydrogen storage materials, such as excessive volume expansion rate caused by uncontrollable lattice distortion, serious cyclic pulverization, and sluggish hydrogen diffusion kinetics, in this embodiment, based on the high hydrogen storage capacity of titanium, zirconium element is introduced to inhibit lattice distortion. When the total molar ratio of titanium to zirconium is less than 0.8, the insufficient titanium content leads to a decrease in hydrogen storage capacity to 1.8 wt%, and the lattice expansion rate is as high as 12%; when it exceeds 1.05, the excessive titanium causes an abnormal increase in lattice constant, and the pulverization rate after cycling increases to 28%. Within the scope defined in claim 9, the main lattice of titanium bears hydrogen atoms, and zirconium disperses stress through local distortion, reducing the volume expansion rate from 24% of the traditional alloy to 6.5%, while the hydrogen storage density is stabilized at 2.3 wt%. Secondly, the addition of zirconium induces the formation of nano-scale zirconia precipitation phases, whose high hardness and low hydrogen solubility inhibit crack propagation. For example, when the molar ratio of titanium to zirconium in the embodiment is 1.05, the cycle life is increased to 16,500 times, which is 175% higher than that of the unbalanced ratio scheme. Finally, zirconium forms a zirconium-rich layer on the surface of the alloy, reducing the hydrogen adsorption barrier, increasing the hydrogen diffusion coefficient, increasing the hydrogen absorption rate by 2.7 times, and shortening the induction period to 8 seconds.

[0115] Embodiment 9:

[0116] In this embodiment, the storage system includes a heat exchanger thermally connected to the heat management path. The heat exchanger is designed with an inclination to the through-hole 25 of the drum 23 of the circulation module 2 to form a turbulent effect. At the same time, through the linkage displacement of the opening 26 of the rotating ring 24 and the connecting frame 27 of the base 21, the change in the channel 51 spacing caused by the deformation of the compensation module 4 is compensated in real time, which helps to maintain a constant contact pressure between the wall surface of the channel 51 and the compensation structure.

[0117] The above are only the preferred embodiments of the present invention, and do not limit the patent scope of the present invention accordingly. Any equivalent structural or equivalent process transformations made by using the content of the specification and drawings of the present invention, or directly or indirectly applied to other related technical fields, are equally included in the patent protection scope of the present invention.

Claims

1. A hydrogen energy storage system, the storage system comprising a housing and a hydrogen energy supply module, characterized in that, The storage system further includes a storage module, a compensation module, and a thermal management module that are coaxially nested inside the housing from the inside to the outside; A circulation module is provided on the side of the thermal management module. The inner liner of the storage module is provided with a corrugated structure. The compensation module includes a compensation structure wound around the outer periphery of the corrugated structure. The housing is provided with a first liquid port, a second liquid port, and a third liquid port. A plurality of flow channels communicating with the first liquid port and the second liquid port are provided in the thermal management module; The circulation module is communicated with the plurality of flow channels. The circulation module includes a control unit. The control unit 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.

2. The hydrogen energy storage system according to claim 1, wherein The plurality of flow channels include pipes spirally wound around the outer periphery of the compensation structure. The openings of the pipes are respectively communicated with the first liquid port and the second liquid port. The third liquid port is provided on one side close to the circulation module. The circulation module is movably provided in the housing.

3. A hydrogen energy storage system according to claim 1, characterized in that, The circulation module includes a base, a circulation member rotatably provided in the base, and a rotating cylinder provided inside the circulation member. The circulation member is an axisymmetric structure. The symmetric side of the circulation member includes a rotating ring rotatably provided with the rotating cylinder. The rotating ring is also rotatably provided in the base.

4. A hydrogen energy storage system according to claim 3, characterized in that, A plurality of through holes are provided on the rotating cylinder. A plurality of openings are provided on the side of the rotating ring close to the rotating cylinder. A connecting frame is provided in the base. The rotating cylinder and the rotating ring are movably provided on the base through the connecting frame and are communicated on the symmetric side through the through holes and the openings.

5. A hydrogen energy storage system according to claim 4, wherein, The plurality of through holes and openings are all inclinedly provided.

6. A hydrogen energy storage system according to claim 1, characterized in that, The corrugated structure includes a compensation metal for providing telescopic compensation ability. 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.

7. A hydrogen energy storage system according to claim 1, characterized in that, The storage module is configured with a hydrogen storage metal for hydrogen storage, and the hydrogen storage metal is composed of Ti at A wt.%, a Mn b Cr c V d Zr e Fe f , La at B wt.%, x Ni y and V at C wt.%, where 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.

8. A hydrogen energy storage system according to claim 6, characterized in that, The compensation structure includes 60-65 wt% of carbon fiber and 35-40 wt% of epoxy resin matrix.

9. A hydrogen energy storage system according to claim 7, characterized in that, The hydrogen storage metal composition satisfies: a + e = 0.8-1.05; b + c + d = 1.8-2.

2.

10. A hydrogen energy storage system according to claim 1, characterized in that, The storage system includes a heat exchanger thermally connected to the thermal management path.

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