Gas-solid composite hydrogen storage hydrogenation station system and refueling control method thereof

Abstract

This invention relates to a gas-solid hybrid hydrogen storage and refueling station system and its refueling control method, belonging to the field of solid-state hydrogen storage technology. It aims to provide a safe, economical, and high-performance hydrogen storage solution for medium-sized hydrogen refueling stations through an innovative solid-dominant gas-solid hybrid architecture. The system includes a gaseous storage module, a solid-state storage module, a buffer storage tank, a refueling device, an unloading station, and a control module. The control module includes a control unit and a monitoring unit. The monitoring unit monitors the refueling flow rate and refueling time of the refueling device in real time and transmits the detected signals back to the control unit. The control unit calculates the hydrogen demand during peak and / or off-peak periods based on the detection signals from the monitoring unit. Before the peak refueling period, it controls the solid-state storage module to release hydrogen into the buffer storage tank in advance and adjusts the hydrogen output ratio between the gaseous and solid-state storage modules. This significantly reduces the safety risks and safety distance requirements of the hydrogen refueling station.

Description

Technical Field

[0001] This invention relates to the field of solid-state hydrogen storage technology, specifically to a gas-solid hybrid hydrogen storage and refueling station system and its refueling control method. Background Technology

[0002] Hydrogen energy, as a highly efficient and zero-carbon emission clean energy carrier, is playing an increasingly important strategic role in the global energy transition. A report by the Hydrogen Council indicates that by 2030, global demand for clean hydrogen energy is expected to grow significantly through the effective implementation of existing policies, with the application of fuel cell vehicles (FCVs) in road transportation being a key driver. FCVs offer advantages such as long driving range, rapid refueling, and zero emissions; however, their large-scale commercial deployment heavily relies on a well-developed hydrogen refueling station (HRS) infrastructure.

[0003] A typical medium-sized hydrogen refueling station needs to have a daily refueling capacity of 1000 kg of hydrogen to support the normal operation of 200–250 35MPa FCVs. Each vehicle needs an average refueling of approximately 4–4.5 kg of hydrogen, with each refueling session strictly controlled within 3–5 minutes. The station must fully comply with international standards, including SAE J2601 (which specifies the hydrogen refueling protocol, covering temperature control, pre-cooling requirements, and safety limits, such as pre-cooling to -40°C to prevent overheating of the vehicle's hydrogen storage tank) and SAE J2799 (a station-vehicle communication protocol that ensures real-time data exchange for accurate filling status monitoring). Furthermore, the hydrogen refueling station must also meet safety design, installation, and operation requirements such as ISO 19880-1.

[0004] Currently, mainstream hydrogen storage technologies are mainly divided into three routes: high-pressure gaseous hydrogen storage, liquid hydrogen storage, and solid-state hydrogen storage. Among them, high-pressure gaseous hydrogen storage (operating pressure 35~70 MPa) technology is the most mature and has been widely used in existing hydrogen refueling stations and FCV on-board hydrogen storage systems. Its outstanding advantage lies in its fast release rate (typical value of about 0.1 kg / s), which can better meet the high-flow refueling demand during peak periods. However, this technology has significant limitations: the volumetric hydrogen storage density is relatively low (about 25 kg H2 / m³), resulting in a large storage tank volume; the explosion risk is relatively high (TNT equivalent of about 0.5 kg / kg H2), and the safety distance requirements are strict (according to NFPA 2, ISO standards, and risk assessments, a large isolation area is required to prevent leakage, fire, or explosion accidents); at the same time, the high-pressure compression process consumes a lot of energy (about 1.8 kWh / kg), maintenance is complex, and the site selection is limited by urban planning and safety regulations.

[0005] In contrast, solid-state hydrogen storage technology primarily utilizes metal hydrides (such as AB2-type alloys like LaNi2, which achieve hydrogen storage through reversible chemisorption) or other solid materials. Its core advantages include: significantly higher volumetric hydrogen storage density (typically above 35 kg H2 / m³, even reaching 90–110 kg H2 / m³); low operating pressure (typically <5 MPa, even close to atmospheric pressure); and excellent intrinsic safety (significantly reduced probability of leakage and explosion consequences, allowing for significantly shorter safety distances and reduced site restrictions and construction costs). Furthermore, solid-state hydrogen storage can operate at room temperature or mild conditions, facilitating transportation and long-term storage. Related research shows that solid-state hydrogen storage in hydrogen refueling station applications can reduce reliance on high-power compressors, thereby lowering overall energy consumption and investment.

[0006] However, solid-state hydrogen storage technology also faces key technical bottlenecks: the hydrogen absorption and desorption kinetics are relatively slow (taking LaNi5 as an example, the absorption rate is about 0.01 kg / s / kg alloy, and the release rate is about 0.005 kg / s / kg alloy, which still requires a long time under heating conditions of 353 K); there is the problem of material degradation during recycling (the capacity decays by about 35% after 1000 hydrogen absorption and desorption cycles, and the effective weight percentage drops to about 0.91 wt%); the thermal effect is significant (the absorption process is exothermic, and the desorption process is endothermic), which places high demands on the heat and mass transfer design of the reactor. If solid-state hydrogen storage is used alone, it is difficult to stably meet the rapid refueling flow rate (60–120 g / s) and time requirements specified in SAE J2601, especially during peak periods (e.g., a peak refueling of 675 kg per day for 12 hours) where response delays are likely to occur.

[0007] Existing gas-solid hybrid hydrogen storage technologies are mostly found in patents and research literature, but they mainly take the following forms: (1) small-scale integration with high-pressure gaseous hydrogen storage as the main component and solid as an auxiliary buffer; (2) simple mixing at the material level or vehicle / portable solid devices; (3) demonstration systems that use metal hydride compressors (MHHC) to assist in hydrogen supply. Although these schemes combine the rapid response of gaseous hydrogen storage with the safety advantages of solid to a certain extent, they generally have problems such as a low solid capacity ratio (difficult to exceed 50%), lack of systematic pre-release and dynamic scheduling mechanisms, and insufficient thermal management integration. They cannot achieve an effective balance between "high solid content dominating storage" and "high-speed refueling" at the scale of hydrogen refueling stations (1000 kg per day).

[0008] This invention was proposed against the backdrop of the rapid development of global hydrogen energy infrastructure and the limitations of existing technologies. It aims to provide a safe, economical and high-performance hydrogen storage solution for medium-sized hydrogen refueling stations through an innovative solid-dominant gas-solid composite architecture. Summary of the Invention

[0009] The purpose of this invention is to provide a gas-solid hybrid hydrogen storage and refueling station system, which aims to provide a safe, economical and high-performance hydrogen storage solution for medium-sized hydrogen refueling stations through an innovative solid-dominant gas-solid hybrid architecture.

[0010] To achieve the above objectives, the technical solution adopted by the present invention is as follows: This invention provides a gas-solid hybrid hydrogen storage and refueling station system, comprising: A gaseous storage module, the gaseous storage module comprising at least one gaseous storage tank; A solid-state storage module, the solid-state storage module comprising at least one solid-state storage tank; A buffer storage tank, wherein the exhaust ends of both the gaseous storage module and the solid storage module are connected to the air inlet end of the buffer storage tank; A dispenser, wherein the air inlet of the dispenser is connected to the exhaust outlet of the buffer storage tank; The unloading station has its exhaust end connected to the air inlet of the gaseous storage module and the solid storage module, respectively, and the air inlet of the unloading station is connected to the exhaust end of the hydrogen transport trailer. The control module includes a control unit and a monitoring unit. The monitoring unit is used to monitor the refueling flow rate and refueling time of the dispenser in real time and to transmit the detected signals back to the control unit. The control unit is used to calculate the hydrogen demand during peak and / or off-peak periods based on the detection signals fed back by the monitoring unit, and to control the solid-state storage module to release hydrogen into the buffer storage tank in advance before the arrival of the peak refueling period, and to adjust the hydrogen output ratio of the gaseous storage module and the solid-state storage module.

[0011] Furthermore, the buffer storage tank is provided with a cooling assembly for cooling the hydrogen gas collected in the buffer storage tank.

[0012] Furthermore, the solid storage tank is also equipped with a refueling unit for directly injecting the hydrogen inside into the vehicle.

[0013] Furthermore, the monitoring unit also includes a function for monitoring the pressure of hydrogen input to the unloading station, and the control component is used to dynamically adjust the ratio of the received hydrogen to be diverted to the gaseous storage module and the solid storage module based on the pressure signal monitored by the monitoring unit.

[0014] Furthermore, it also includes a reflux assembly, which is provided with a hydrogen reflux inlet that cooperates with the dispenser.

[0015] Furthermore, the solid-state storage module is also equipped with a conveying component for unidirectionally conveying hydrogen gas within it to the gaseous storage module.

[0016] Furthermore, it also includes an electricity price monitoring unit and a photovoltaic and / or wind power hydrogen production module. The electricity price monitoring unit is used to monitor the current electricity price in real time, and the control unit is used to receive the real-time signal monitored by the electricity price monitoring unit, thereby controlling the hydrogen produced by the photovoltaic and / or wind power hydrogen production module to be diverted to the gaseous storage module and the solid-state storage module.

[0017] This invention also provides a method for controlling the refueling of a gas-solid hybrid hydrogen storage and refueling station system, comprising the following steps: Step 1: Monitor the refueling flow rate and refueling time of the dispenser in real time, and calculate the hydrogen demand during peak and / or off-peak periods based on the monitoring data; Step 2: Based on the peak and / or off-peak hydrogen demand, control the solid-state storage module to start before the peak refueling period arrives, and release hydrogen in advance to mix with the hydrogen released by the gaseous storage module; Step 3: The hydrogen gas collected in the buffer storage tank is added to the vehicle through the filler.

[0018] Furthermore, in step two, before the peak refueling period arrives, the ratio of hydrogen output from the gaseous storage module and the solid storage module to the buffer storage tank is adjusted.

[0019] Due to the application of the above technical solution, the present invention has the following advantages compared with the prior art: The gas-solid hybrid hydrogen storage and refueling station system of the present invention increases the proportion of solid metal hydride hydrogen storage units to 70%~90% or more (operating pressure controlled at <5 MPa, or even as low as 0.1~ MPa), while retaining only small-capacity high-pressure gaseous buffer units (10~30% of the capacity). This fundamentally reduces the exposure of high-pressure gaseous hydrogen, thereby significantly reducing the probability of leaks, fires and explosions, shortening the safety distance, reducing land occupation and insurance costs, and making hydrogen refueling stations easier to deploy in cities or densely populated areas.

[0020] This invention introduces a "dynamic pre-release protocol + gaseous buffer synergy" mechanism, which heats and releases hydrogen from the solid-state storage module 1-2 hours before the peak period, pre-storing the hydrogen in a small-capacity gaseous buffer tank. During the peak period, the gaseous buffer unit dominates the rapid release (release rate at the level of 0.1 kg / s), while the solid-state storage module serves as a stable supplement or the main force during off-peak periods. Thus, even with a high proportion of solid-state components, the refueling time and flow rate requirements specified in SAE J2601 and SAE J2799 can still be stably met. Attached Figure Description

[0021] The following sections will describe some specific embodiments of the invention in detail by way of example and not limitation, with reference to the accompanying drawings. The same reference numerals in the drawings denote the same or similar parts or portions. Those skilled in the art should understand that these drawings are not necessarily drawn to scale. In the drawings: Figure 1 This is a control flow diagram in Embodiment 1 of the present invention; Figure 2 This is a control flow diagram in Embodiment 2 of the present invention; Figure 3 This is a control flow diagram in Embodiment 3 of the present invention; Figure 4 This is a control flow diagram in Embodiment 4 of the present invention. Detailed Implementation

[0022] The technical solution of the present invention will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0023] Furthermore, the technical features involved in the different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other. Example 1

[0024] refer to Figure 1 This invention provides a gas-solid hybrid hydrogen storage and refueling station system, comprising a gaseous storage module, a solid-state storage module, a buffer storage tank, a dispenser, an unloading station, and a control module. The gaseous storage module includes at least one gaseous storage tank, and the solid-state storage module includes at least one solid-state storage tank. The exhaust ends of both the gaseous and solid-state storage tanks are connected to the inlet end of the buffer storage tank. In this example, one gaseous storage tank and one solid-state storage tank are provided.

[0025] refer to Figure 1 The gaseous storage tank is configured as a small-capacity, high-pressure (35 MPa) gaseous buffer tank, which is responsible for rapid storage and release, serving as a buffer accelerator for rapid response during peak periods. Its hydrogen storage capacity accounts for 10% to 30% of the hydrogen storage capacity in the hydrogen refueling station system. The total capacity of each individual gaseous buffer tank is 400 kg to 800 kg. In this embodiment, a 600 kg capacity is used, with three 10 m³ composite tanks. The volume density is approximately 20 kg H2 / m³ to 25 kg H2 / m³, and the SOC threshold is controlled at 0.1 to 0.9 (dynamically adjustable). It is monitored in real time by a pressure sensor (accuracy 0.01 MPa), with a release rate of 0.1 kg / s, which can quickly respond to peak refueling demand.

[0026] refer to Figure 1 The solid-state storage module uses solid metal hydride hydrogen storage units (mainly LaNi5 or Ti-based alloys) as the primary storage medium, accounting for 70%~90% of the hydrogen storage capacity in the hydrogen refueling station system. The operating pressure is controlled at <5 MPa, and the bulk density is approximately 35 kg H2 / m³. The reaction principle is as follows: The solid-state storage tank is equipped with a temperature sensor and an electric heater (353 K, 0.1 kWh / kg), supporting pre-release operation with an absorption rate of approximately 0.01 kg / s / kg alloy. The release rate is increased by preheating. Furthermore, the solid-state storage module is equipped with a delivery component for transferring hydrogen from the solid-state storage module to the gaseous storage module. This is achieved through a bidirectional low-pressure to high-pressure conversion pipeline, enabling dynamic replenishment of low-pressure hydrogen from the solid-state storage module to the gaseous buffer unit.

[0027] refer to Figure 1 In terms of hydrogen storage, the above architecture uses solid-state storage tanks as the main storage medium, while gaseous storage tanks serve as buffers and accelerators for rapid response during peak periods. Through bidirectional low-pressure to high-pressure conversion pipelines, low-pressure hydrogen from the solid-state storage module is dynamically replenished to the gaseous buffer unit. This is fundamentally different from existing composite systems that are dominated by gaseous or assisted by solid-state, significantly reducing the proportion of high-pressure gaseous hydrogen stored and the risk of exposure, and solving the problem of strict safety distance restrictions from the source.

[0028] refer to Figure 1 The buffer storage tank is configured as a 200 kg, 8 m³ buffer tank (35 MPa) to collect hydrogen discharged from the gaseous storage tank and the solid storage tank. The buffer storage tank is equipped with a cooling component to cool the hydrogen collected in the buffer storage tank. The hydrogen in the buffer storage tank is pretreated by the cooling component (–40°C, 0.45 kWh / kg, in compliance with SAE J2601) to ensure refueling safety.

[0029] refer to Figure 1The injector's inlet is connected to the outlet of the buffer storage tank, allowing hydrogen from the buffer storage tank to be injected into the vehicle. The injector's flow rate is 60 g / s to 120 g / s, with an average of 108 g / s primarily supplied by the gaseous buffer and supplemented by solid hydrogen at 12 g / s to 24 g / s. A single injection takes 3 to 5 minutes and supports 200 to 250 vehicles per day, conforming to the SAE J2799 station-vehicle communication protocol. One to two hours before peak injection times, the control module adjusts the ratio of hydrogen output from the gaseous and solid storage tanks, concentrating it into the buffer storage tank. During peak injection times, the gaseous storage tank provides rapid injection, supplemented by the solid storage tank. During off-peak times, the solid and gaseous storage tanks supply hydrogen in equal proportions, or the solid storage tank supplies hydrogen solely.

[0030] refer to Figure 1 The exhaust end of the unloading station is connected to the air inlet of the gaseous storage module and the solid storage module, respectively. The hydrogen input of the unloading station mainly comes from hydrogen transport trailers. The nominal pressure of the hydrogen transport trailers is 20 MPa, with a range of 15 MPa to 25 MPa. Each trailer carries 350 kg, and 3 to 4 trailers are transported per day. The air inlet of the unloading station is connected to the exhaust end of the hydrogen transport trailers through a pipeline.

[0031] refer to Figure 1 The control module includes a control unit and a monitoring unit. The monitoring unit monitors the dispensing flow rate and dispensing time of the dispenser in real time and transmits the detected signals back to the control unit. The control unit uses a PLC control unit combined with an AI control system. The main functions of the control unit include: dynamic SOC calculation and threshold management, input diversion optimization, pre-release protocol triggering, output ratio scheduling, and safety warning. The hydrogen balance relationship meets V he,t = V g,t + V s,t SOC t = SOC {t-1} +Input quantity / capacity – Output quantity / capacity.

[0032] refer to Figure 1 The control unit calculates the hydrogen demand during peak and / or off-peak periods based on the detection signals fed back by the monitoring unit. One to two hours before the peak refueling period, the buffer storage tank is preheated (temperature controlled at approximately 353 K, using electric heating or waste heat from the fuel cell). This releases some hydrogen in advance and stores it in the buffer storage tank. The control unit also adjusts the hydrogen output ratio between the gaseous storage module and the solid-state storage module. During peak periods, the gaseous storage module dominates the rapid release, while the solid-state storage module provides continuous replenishment. During off-peak periods, the solid-state storage module primarily outputs hydrogen directly. Therefore, a refueling unit is also installed on the solid-state hydrogen storage tank for directly refueling the vehicle with the hydrogen stored within.

[0033] refer to Figure 1 Therefore, by controlling the gaseous storage module to release hydrogen rapidly, and the solid storage module to continuously replenish it, the solid storage module will directly output hydrogen during low-temperature periods. This pre-release protocol and buffer coordination mechanism effectively overcome the inherent defect of slow release rate of solid hydrogen storage, ensuring that the single refueling time is stably controlled within 3 to 5 minutes, meeting the SAE J2601 flow requirements, while avoiding energy waste caused by real-time heating.

[0034] refer to Figure 1 In addition, the system also includes a reflux assembly, which is used to reflux excess hydrogen collected in the buffer storage tank, that is, to recover unfilled or residual hydrogen through the recovery system, with the loss rate controlled within 2%.

[0035] refer to Figure 1 The above-mentioned solid-state combined hydrogen storage and refueling station system refueling control method includes the following steps: Step 1: Monitor the refueling flow rate and refueling time of the dispenser in real time, and calculate the hydrogen demand during peak and / or off-peak periods based on the monitoring data; Step 2: Based on the peak and / or off-peak hydrogen demand, control the solid-state storage module to start before the peak refueling period arrives, and release hydrogen into the buffer storage tank in advance to mix with the hydrogen released by the gaseous storage module; at the same time, before the peak refueling period arrives, adjust the ratio of hydrogen output from the gaseous storage module and the solid-state storage module to the buffer storage tank. Step 3: The hydrogen gas collected in the buffer storage tank is added to the vehicle through the filler.

[0036] refer to Figure 1 The following explanation uses a complete process simulating the daily refueling of approximately 1000 kg of hydrogen as an example: Starting with unloading hydrogen from a long-haul hydrogen transport truck (assuming 3-4 trucks per day supplying a total of 1000 kg, operating during peak periods), considering the pressure drop during unloading (trailer pressure drops from 20 MPa to 15 MPa, input rate decreases by 10%, and flow adjustment), the initial SOC is 0.5 for the gaseous storage module and 0.5 for the solid-state storage module; the AI ​​control system updates every 10 minutes; the daily peak is 150 trucks (675 kg), and the off-peak is about 72 trucks (325 kg), totaling 222 trucks, with a total refueling volume of about 1000 kg. The total system capacity is designed as follows: the total capacity of the gaseous storage module is 600 kg (35 MPa), and the total capacity of the solid-state storage module is 1400 kg (<5 MPa), with the solid-state capacity accounting for 70%.

[0037] Step 1: Unloading and inputting air (time 0-45 min, first tow truck): A hydrogen transport trailer (350 kg, initial 20 MPa) connects to the unloading station. The pressure reducing valve adjusts the pressure drop (5 MPa / h), diverting 75% to the gaseous storage module (262.5 kg, compressed to 1.8 kWh / kg, 472.5 kWh) and 25% to the solid-state storage module (87.5 kg, 3 MPa, pressure drop adjustment increased by 5%). The pressure drop causes a 10% decrease in the input rate (from 0.1 kg / s to 0.09 kg / s). The AI ​​control system increases the gas intake of the solid-state storage module by 5%. The initial mass of the gaseous storage module is 300 kg, which increases to 562.5 kg after adding 262.5 kg, raising the SOC of the gaseous storage module to 0.9375. The initial mass of the solid-state storage module is 700 kg, which increases to 787.5 kg after adding 87.5 kg, raising the SOC of the solid-state storage module to 0.5625.

[0038] Step 2: Storage and Conversion (45 min - 3 h): The gaseous storage module stored 262.5 kg, with a SOC of 0.9375 (below the safety threshold of 0.95) and no transfer. The solid-state storage module absorbed 87.5 kg (0.01 kg / s / kg, requiring approximately 2.5 h). The AI ​​control system regulated the process: electric heating at 293 K (∆Ha=-28 kJ / mol, 12 kWh). The SOC of the gaseous storage module remained stable at 0.9375, while the SOC of the solid-state storage module was 0.5625.

[0039] Step 3: Buffer pretreatment (3-3.5 h): The manifold buffer storage tank (200 kg) has the following proportions: 80% of the hydrogen comes from the gaseous storage module and 20% comes from the solid-state storage module (i.e., 210 kg gaseous + 52.5 kg solid). It is pre-cooled to -40°C (0.45 kWh / kg, 118 kWh). The residual pressure drop affects the buffer pressure drop by 1 MPa. The AI ​​control system then adjusts the hydrogen supply to 85% from the gaseous storage module and 15% from the solid-state storage module (because the gaseous SOC > 0.9). The flow valve is set at 0.01 kg / s. After the gaseous storage module outputs 210 kg of hydrogen, 352.5 kg remains with an SOC of 0.5875. After the solid-state storage module outputs 52.5 kg of hydrogen, 735 kg remains with an SOC of 0.525.

[0040] Step 4: Refueling and Output (3.5 h-7 h, first batch of vehicles): The refueling speed is 60~120 g / s, and the refueling rate is 4.5 kg / vehicle. For the first FCV: the gaseous storage module is in control (80%, 3.6 kg, 3 min). The SOC of the gaseous storage module decreases by 0.006. The AI ​​control system controls the solid-state storage module to release 0.9 kg (0.005 kg / s / kg) of hydrogen. This process is repeated for 30 vehicles (135 kg, 1 h). The cumulative output of the 30 vehicles is: 108 kg of hydrogen from the gaseous storage module and 27 kg of hydrogen from the solid-state storage module. The gaseous storage module has 244.5 kg of hydrogen remaining with an SOC of 0.4075, and the solid-state storage module has 708 kg of hydrogen remaining with an SOC of 0.5057.

[0041] Step 5: Unloading the gas with the second trailer (7-7.5 hours): The second hydrogen transport trailer (350 kg, initial 20 MPa) unloads hydrogen, diverting 262.5 kg of hydrogen to the gaseous storage module and 87.5 kg of hydrogen to the solid-state storage module, for a total input of 700 kg of hydrogen. The gaseous storage module increases its hydrogen capacity by 262.5 kg to 507 kg, with a SOC of 0.845, while the solid-state storage module increases its hydrogen capacity by 87.5 kg to 795.5 kg, with a SOC of 0.5682.

[0042] Step 6: Continue storing, converting, and buffering (7.5-9 hours): The second batch of 350 kg was stored. The solid-state storage module absorbed 87.5 kg of hydrogen, buffered and pre-cooled the second batch. The SOC of the gaseous storage module was 0.845, and the SOC of the solid-state storage module was 0.5682.

[0043] Step 7: Continue adding fuel (9-13 hours, peak): 90 vehicles (405 kg) were refueled. The gaseous storage module accounted for 80% (324 kg), and the solid storage module supplemented 20% (81 kg). The gaseous storage module had 183 kg remaining with a SOC of 0.305; the solid storage module had 714.5 kg remaining with a SOC of 0.5104. Regulation: The AI ​​control system detected that the SOC of the gaseous storage module was too low, so it pre-released 50 kg of solid-state storage module (2h, 20 kWh heating) into the gaseous storage module. After the pre-release: the solid-state storage module had 664.5 kg remaining and an SOC of 0.4746; the gaseous storage module increased by 50 kg to 233 kg and had an SOC of 0.3883.

[0044] Step 8: The third trailer unloads the gas (13-13.5 hours): The third trailer (310 kg, pressure drop effect rate 0.085 kg / s) diverts 232.5 kg of hydrogen to the gaseous storage module and 77.5 kg of hydrogen to the solid-state storage module (maintaining a 75% / 25% ratio), for a total input of 1010 kg (close to 1000 kg). The hydrogen in the gaseous storage module increases by 232.5 kg to 465.5 kg, with an SOC of 0.7758; the hydrogen in the solid-state storage module increases by 77.5 kg to 742 kg, with an SOC of 0.53.

[0045] Step 9: Final storage conversion and buffering (13.5-15 hours): The storage capacity is 310 kg, the solid-state storage module absorbs 77.5 kg, the buffer accumulates the remainder, and it is pre-cooled. The SOC of the gaseous storage module is 0.7758, and the SOC of the solid-state storage module is 0.53.

[0046] Step 10: Filling complete (15-20 hours, low point): 100 vehicles were refueled (450 kg each, 4.5 kg per vehicle). The solid-state storage module and the gaseous storage module each accounted for 50% (225 kg gaseous + 225 kg solid). The gaseous storage module output 225 kg → 465.5 - 225 = 240.5 kg, SOC = 240.5 / 600 ≈ 0.4008; the solid-state storage module output 225 kg → 742 - 225 = 517 kg, SOC = 517 / 1400 ≈ 0.3693. For the last FCV: the gaseous storage module output 2.25 kg of hydrogen, and the solid-state storage module output 2.25 kg of hydrogen. The refueling time was 4 minutes. After refueling, the vehicle left.

[0047] In summary, regarding safety, the solid-state storage module's low-pressure operation (<5 MPa) buffers the high-pressure risks of the gaseous storage module, reducing the TNT equivalent by 25-40% and the leakage probability by 40%, meeting the ISO 19880-1 standard. This hybrid approach can reduce the accident rate to 0.1%, especially in urban environments, where calculations show hazardous operation time reduced to 3%. The MEA alloy further enhances the absence of explosion risk, fundamentally reducing exposure to high-pressure gaseous hydrogen, thereby significantly reducing the probability of leaks, fires, and explosions, shortening safety distances, reducing land occupation and insurance costs, and making hydrogen refueling stations easier to deploy in urban or densely populated areas.

[0048] In terms of efficiency, the combination of rapid release (0.1 kg / s) from the gaseous storage module and high-density storage (35 kg / m³) from the solid-state storage module achieves an overall efficiency of 86-96%, far exceeding that of a single mode (75-85% gaseous, 80-90% solid). This integration reduces energy loss by 10% through dynamic ratio adjustment (peak 80% gaseous + 20% solid), reducing compression energy consumption to 1.8 kWh / kg and pre-cooling to 0.45 kWh / kg, with a total energy consumption of approximately 1840 kWh / day (after pressure drop optimization). This mode can reduce the hydrogen abandonment rate in hydrogen refueling stations to below 1.5%, which is 1.5 times lower than traditional gaseous systems. Furthermore, verification results show that the stable fluctuation of SOC is less than 10%, and the energy consumption distribution is balanced (compression accounts for 73%, pre-cooling 24%), demonstrating sustainability.

[0049] Furthermore, this invention introduces a "dynamic pre-release protocol + gaseous buffer synergy" mechanism, preheating and releasing hydrogen from the solid-state storage module 1-2 hours before peak periods. This pre-stores hydrogen in a small-capacity gaseous buffer tank, allowing the gaseous buffer unit to dominate rapid release during peak periods (release rate on the order of 0.1 kg / s), while the solid-state storage module serves as a stable supplement or the main force during off-peak periods. This ensures that even with a high solid-state ratio, the refueling time and flow rate requirements specified in SAE J2601 and SAE J2799 can still be stably met. Therefore, the significant advantage of the gas-solid mixing process lies in its synergistic and complementary mechanism, effectively integrating the rapid response of the gaseous storage module with the high-density storage and low-pressure safety characteristics of the solid-state storage module (solid-state capacity ratio can reach over 70%).

[0050] This invention improves the absorption / release rate of solid-state storage modules to approximately 0.012 kg / s / kg and controls the degradation rate to within 20% by integrating efficient heat transfer structures (fins, heat pipes, phase change materials), modified alloy optimization (Mn / Co / Al element substitution or MEA type alloys) and fuel cell waste heat recovery mechanisms. At the same time, it significantly reduces compression energy consumption, maintains the overall system efficiency at 86-96%, controls the total daily energy consumption at around 1840 kWh, and reduces the hydrogen loss rate to less than 1.5%.

[0051] This invention employs an intelligent control system combining PLC and AI (updated every 5-10 minutes, integrating genetic algorithms or demand prediction models) to achieve dynamic optimization of input diversion ratio (70-90% directly low-pressure distribution to the solid-state storage module during trailer unloading), real-time SOC monitoring (0.1-0.9 for gaseous units (dynamically adjustable to 0.95), 0.2-0.9 for solid-state storage modules), and pre-release scheduling. This ensures that the system can maintain a stable SOC fluctuation of less than 10% even under input fluctuation conditions, and effectively reduces dangerous operation time.

[0052] This invention proposes a modular system design (input module, solid-state storage module, gaseous storage module, buffer pretreatment module, and refueling unit), and deeply integrates a high solid-state ratio architecture, a pre-release buffer mechanism, thermal management optimization, and AI closed-loop control to form a complete technical solution that can be scaled up (supporting expansion to 5000 kg / day). Example 2

[0053] refer to Figure 2 The content and structure of this embodiment are basically the same as those of Embodiment 1, except that: This embodiment focuses on addressing the problem of decreased input rate caused by input pressure fluctuations (15–25 MPa) in long-tube trailers, and verifies the robustness of the system under unsteady input conditions.

[0054] Specifically, when the pressure of the long-tube trailer gradually decreases from the nominal 20 MPa to 15 MPa, the input rate will decrease by about 10%. If no adjustment is made, it may lead to insufficient replenishment of the gas buffer unit, affecting the refueling flow rate during peak periods.

[0055] Therefore, in this embodiment, the monitoring unit also includes a component for monitoring the pressure of hydrogen input to the unloading station, and a control component for dynamically adjusting the ratio of the hydrogen received by the unloading station to the gaseous storage module and the solid storage module based on the pressure signal monitored by the monitoring unit.

[0056] This embodiment uses an AI control system to monitor the trailer's pressure, flow rate, and SOC status in real time, dynamically adjusting the flow ratio by controlling the opening of the pressure reducing valve (98% efficiency) and the flow control valve (0.01 kg / s accuracy). For example, when the SOC threshold of the gaseous storage module is low, 60%~80% of the hydrogen can be compressed and sent into the gaseous storage module to quickly build up reserves. When the SOC threshold of the gaseous storage module reaches the target value, 70%~90% of the hydrogen is sent at low pressure (about 3 MPa) directly into the solid-state storage module for slow absorption, reducing reliance on the high-pressure compressor. If necessary, the released hydrogen is preferentially transferred to the gaseous buffer tank by triggering the solid-state storage module's pre-release protocol in advance (starting electric heating to 353 K 1.5–2 hours in advance, with heating energy consumption controlled within 0.1 kWh / kg).

[0057] The specific operating principle is as follows: Pressure drop detection phase (10-30 minutes after unloading begins): When the flow control valve detects a decrease in the input rate, the AI ​​control system immediately calculates the compensation requirement and increases the solid-state diversion ratio of subsequent trailer unloading by 10-15 percentage points.

[0058] Pre-release compensation phase (started immediately after pressure drop occurs): The solid-state storage module releases approximately 100–150 kg of hydrogen to the gaseous storage module in advance during off-peak or transitional periods to ensure that the gaseous storage module's SOC remains at a high availability level of 0.6–0.8.

[0059] Peak period betting verification: Even with a 15-20 minute extension in total input time, peak refueling still maintains the gaseous storage module as the dominant force (around 108 g / s), with the solid storage module supplementing at 12 g / s to 24 g / s. The refueling time for a single refueling session remains stable within 3 to 5 minutes, and no flow bottleneck is observed.

[0060] Energy consumption and safety indicators: This dynamic adaptation strategy reduces compression energy consumption by approximately 12% to 15% compared to the uncompensated scenario, while keeping hydrogen loss rate below 1.5%. The SOC of the gaseous storage module never exceeds the safety threshold of 0.8, and the proportion of hazardous operation time is reduced to below 3%.

[0061] This embodiment fully demonstrates that even in the most common trailer pressure drop scenario in actual operation, the system can still maintain refueling performance through AI control system prediction and pre-release coordination, demonstrating high engineering robustness and adaptability. This method is particularly suitable for areas with unstable hydrogen supply chains or hydrogen refueling stations with frequent trailer dispatch. Example 3

[0062] refer to Figure 3 The content and structure of this embodiment are basically the same as those of Embodiment 1, except that: This embodiment verifies the scalability of the modular architecture and control strategy for application scenarios where the system is expanded to a larger scale (5000 kg refueling capacity per day), while maintaining the high security advantages of solid-state dominance.

[0063] When expanding to a daily refueling capacity of 5,000 kg (supporting approximately 1,000–1,250 FCVs), the solid-state storage module capacity will remain at 75%–85% (the total effective solid-state capacity will increase accordingly to 1,200–1,500 kg), while the gaseous storage module capacity will increase proportionally to 800 kg–1,200 kg (still controlled within 15–25% of the total capacity).

[0064] This embodiment adopts a multi-module parallel design: the solid storage module consists of multiple parallel solid storage tanks (each group has a capacity of 300–500 kg), the gaseous storage module consists of multiple groups of small gaseous storage tanks connected in parallel, and the buffer storage tank is correspondingly expanded to a capacity of 800 kg to 1000 kg.

[0065] The key expansion measures and operational characteristics are as follows: Modular parallel operation and independent control: Each solid storage tank can independently perform hydrogen absorption and release operations, and the AI ​​control system enables alternating pre-release to avoid overloading of a single reactor; the gaseous storage tanks are managed in groups to ensure that at least two groups are in a high SOC available state at any time.

[0066] AI scheduling optimization and upgrade: The prediction model window has been extended to 30-60 minutes, and a multi-objective genetic algorithm is used to simultaneously optimize the diversion ratio, pre-release timing, pre-cooling energy consumption, and SOC balance. During peak periods (assuming that the daily peak refueling volume accounts for 65-70% of the total), the dominant ratio of gaseous storage tanks is adjusted to 75-85%, and the supplementary ratio of solid storage tanks is correspondingly increased but still maintains a secondary role.

[0067] Thermal management and energy consumption control: The total energy consumption increases proportionally after expansion, but the energy consumption per unit of hydrogen remains at around 1.8~1.9 kWh / kg. By adding a waste heat recovery interface (coupled with the waste heat of fuel cells or electrolyzers), the preheating energy consumption is controlled within 8~10% of the total energy consumption.

[0068] Performance verification indicators: After expansion, the overall system efficiency remains at 86-95%, SOC fluctuation is <12% (slightly relaxed but still within the safe range), single refueling time is stable at 3.5-5 minutes, and hydrogen loss rate is ≤1.8%. Safety assessment shows that due to the further reduction in the proportion of high-pressure gaseous buffer capacity, the overall explosion risk is reduced by 35-45% compared to the traditional all-gas system, and the safety distance requirement is significantly better than that of a conventional 5000 kg-class hydrogen refueling station.

[0069] Economic and maintenance advantages: Modular design allows for online maintenance of individual modules without downtime; the high proportion of solid-state storage modules extends the long-term material replacement cycle, and maintenance costs are reduced by about 20-25% compared to traditional gaseous storage module-dominated systems. Example 4

[0070] refer to Figure 4 The content and structure of this embodiment are basically the same as those of Embodiment 1, except that: It also includes an electricity price monitoring unit and photovoltaic and / or wind power hydrogen production components. The electricity price monitoring unit is used to monitor the current electricity price in real time, and the control unit is used to receive the real-time signal monitored by the electricity price monitoring unit, thereby controlling the hydrogen produced by the photovoltaic and / or wind power hydrogen production components to be diverted to the gaseous storage module and the solid-state storage module. The AI ​​control system can further predict the real-time electricity price and hydrogen production power, and prioritize the allocation of low-pressure hydrogen to the solid-state storage module to further reduce compression energy consumption.

[0071] The above embodiments are only for illustrating the technical concept and features of the present invention. Their purpose is to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be used to limit the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A gas-solid hybrid hydrogen storage and refueling station system, characterized in that, include: A gaseous storage module, the gaseous storage module comprising at least one gaseous storage tank; A solid-state storage module, the solid-state storage module comprising at least one solid-state storage tank; A buffer storage tank, wherein the exhaust ends of both the gaseous storage module and the solid storage module are connected to the air inlet end of the buffer storage tank; A dispenser, wherein the air inlet of the dispenser is connected to the exhaust outlet of the buffer storage tank; The unloading station has its exhaust end connected to the air inlet of the gaseous storage module and the solid storage module, respectively, and the air inlet of the unloading station is connected to the exhaust end of the hydrogen transport trailer. The control module includes a control unit and a monitoring unit. The monitoring unit is used to monitor the refueling flow rate and refueling time of the dispenser in real time and transmit the detected signals back to the control unit. The control unit is used to calculate the hydrogen demand during peak and / or off-peak periods based on the detection signals fed back by the monitoring unit, control the solid-state storage module to release hydrogen into the buffer storage tank in advance before the arrival of the peak refueling period, and adjust the hydrogen output ratio of the gaseous storage module and the solid-state storage module.

2. The gas-solid composite hydrogen storage and refueling station system according to claim 1, characterized in that, The buffer storage tank is equipped with a cooling component for cooling the hydrogen gas collected in the buffer storage tank.

3. The gas-solid composite hydrogen storage and refueling station system according to claim 1 or 2, characterized in that, The solid storage tank is also equipped with a refueling unit for directly adding hydrogen gas into the vehicle.

4. The gas-solid composite hydrogen storage and refueling station system according to claim 3, characterized in that, The monitoring unit also includes a function to monitor the pressure of hydrogen input to the unloading station. The control component is used to dynamically adjust the ratio of the received hydrogen to be diverted from the unloading station to the gaseous storage module and the solid storage module based on the pressure signal monitored by the monitoring unit.

5. The gas-solid composite hydrogen storage and refueling station system according to claim 4, characterized in that, It also includes a reflux assembly, which has a hydrogen reflux inlet that cooperates with the dispenser.

6. The gas-solid composite hydrogen storage and refueling station system according to claim 5, characterized in that, The solid-state storage module is also equipped with a conveying component for unidirectionally conveying hydrogen gas into the gaseous storage module.

7. The gas-solid composite hydrogen storage and refueling station system according to claim 5, characterized in that, It also includes an electricity price monitoring unit and a photovoltaic and / or wind power hydrogen production module. The electricity price monitoring unit is used to monitor the current electricity price in real time, and the control unit is used to receive the real-time signal monitored by the electricity price monitoring unit, thereby controlling the hydrogen produced by the photovoltaic and / or wind power hydrogen production module to be diverted to the gaseous storage module and the solid-state storage module.

8. A method for controlling the refueling of a gas-solid hybrid hydrogen storage and refueling station system, characterized in that, Includes the following steps: Step 1: Monitor the refueling flow rate and refueling time of the dispenser in real time, and calculate the hydrogen demand during peak and / or off-peak periods based on the monitoring data; Step 2: Based on the peak and / or off-peak hydrogen demand, control the solid-state storage module to start before the peak refueling period arrives, and release hydrogen in advance to mix with the hydrogen released by the gaseous storage module; Step 3: The hydrogen gas collected in the buffer storage tank is added to the vehicle through the filler.

9. The method for controlling the refueling of a gas-solid composite hydrogen storage and refueling station system according to claim 8, characterized in that, In step two, before the peak refueling period arrives, the ratio of hydrogen output from the gaseous storage module and the solid storage module to the buffer storage tank is adjusted.

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