Hydrogen desorption control method for solid-state hydrogen storage and supply and solid-state hydrogen storage and supply system

Abstract

The invention discloses a hydrogen desorption control method for solid-state hydrogen storage and supply. The method comprises the steps that the current pressure and the current temperature of a solid-state hydrogen storage and supply system are obtained; determining a hydrogen desorption temperature corresponding to the current hydrogen content value and the hydrogen desorption balance pressure, and calculating to obtain an adjusting temperature according to the hydrogen desorption temperature and the current temperature; and adjusting the temperature of the solid hydrogen storage and supply system to the adjusting temperature. The invention further discloses a solid-state hydrogen storage and supply system using the method, the system comprises at least one hydrogen storage bottle, a temperature adjusting device, a temperature detection device, a pipeline, a pressure detection device, a switch component and a control device, and the control device is configured to receive the current temperature and the current pressure, determine the hydrogen desorption temperature, calculate the adjusting temperature and control the hydrogen desorption temperature according to the adjusting temperature. The switch is used for controlling the temperature adjusting device to adjust the temperature and controlling the switch component.

Description

Technical Field

[0001] The present invention relates to the technical field of solid-state hydrogen storage and supply, and in particular to a hydrogen release control method for solid-state hydrogen storage and supply and a solid-state hydrogen storage and supply system. Background Art

[0002] As an ideal energy carrier, hydrogen energy is an important energy implementation method for achieving the goals of carbon peak and carbon neutrality. However, the storage and supply of hydrogen is one of the key bottlenecks restricting the application of the hydrogen energy industry. The current hydrogen storage methods are mainly high-pressure gas hydrogen, liquid hydrogen and solid hydrogen storage. However, both high-pressure gas hydrogen and liquid hydrogen have disadvantages such as high safety risks, low volume hydrogen storage density, and high energy consumption for pressurization / liquefaction. Liquid hydrogen also has the problem of being volatile and difficult to store for a long time, which limits the promotion and use of high-pressure gas hydrogen and liquid hydrogen. Solid-state hydrogen storage is a hydrogen storage technology based on solid-state hydrogen storage materials. It has the advantages of high volume hydrogen storage density, moderate operating temperature and pressure, long-term storage of hydrogen, and high safety. It is considered to be one of the main ways of hydrogen storage in the future. It has broad application prospects in the fields of on-board hydrogen storage systems, energy storage power generation, and hydrogen refueling stations for vehicles such as automobiles and ships.

[0003] As an on-board hydrogen storage system, in small hydrogen fuel cell vehicles (such as tricycles, two-wheelers, four-wheel passenger cars, etc.), the hydrogen system (such as fuel cells, hydrogen internal combustion engines, etc.) has high requirements for hydrogen supply pressure and rate, and the hydrogen release rate of solid hydrogen storage materials decreases significantly with the decrease of temperature and hydrogen content. On the one hand, it leads to the problem of being unable to start at low temperature, and on the other hand, after a long period of hydrogen release, the hydrogen release rate and pressure of the hydrogen storage and supply system cannot stably meet the requirements of the hydrogen system. This causes the room temperature solid-state hydrogen storage and supply system to be unable to meet the application requirements in room temperature scenarios. In actual application scenarios, the temperature change is not a stable or predictable state, which makes the hydrogen supply pressure unstable under unknown temperature or large temperature changes, affecting the application and popularization of solid-state hydrogen storage materials. The current technology uses hydrogen storage alloys with high hydrogen release platform pressure as hydrogen storage media, which can quickly release hydrogen in the range of -10 to 30 ° C. However, at an ambient temperature of 65 ° C (for example, the hydrogen system can reach this temperature after being exposed to direct sunlight for a period of time), it is very easy to increase the pressure to more than 10 MPa, resulting in excessive pressure in the hydrogen storage and supply system, which poses a high safety risk. Using hydrogen storage materials with lower equilibrium pressure will significantly improve safety in high temperature ranges, but will lead to seriously insufficient hydrogen release rate at low or even room temperature.

[0004] Therefore, technical personnel in this field are committed to developing a hydrogen release control method and a solid-state hydrogen storage and supply system for solid-state hydrogen storage and supply, which are more environmentally adaptable, can effectively control the temperature of the hydrogen storage and supply system, and realize stable and rapid hydrogen supply of the hydrogen storage and supply system. At the same time, the application of medium and low pressure hydrogen storage alloys avoids the risk of system overpressure at ambient temperature. Summary of the invention

[0005] To achieve the above object, the present invention provides a method for controlling hydrogen release in a solid-state hydrogen storage and supply, comprising:

[0006] Obtain the current pressure and current temperature of the solid-state hydrogen storage and supply system;

[0007] Determine the dehydrogenation temperature corresponding to the current hydrogen content value and the preset pressure value, and calculate the adjustment temperature according to the dehydrogenation temperature and the current temperature;

[0008] The temperature of the solid-state hydrogen storage and supply system is adjusted to the adjustment temperature.

[0009] Furthermore, the hydrogen release control method further comprises:

[0010] Before calculating the adjustment temperature, determine whether the temperature of the solid-state hydrogen storage and supply system needs to be adjusted.

[0011] Furthermore, the hydrogen release control method further comprises:

[0012] The current pressure is compared with a preset pressure value. When the current pressure is greater than the preset pressure value, the temperature of the solid-state hydrogen storage and supply system is stopped from being increased. When the current pressure is less than or equal to the preset pressure value, the adjustment temperature is calculated according to the hydrogen release temperature and the current temperature.

[0013] Furthermore, the temperature regulating device is controlled to regulate the temperature of the solid-state hydrogen storage and supply system to the regulating temperature.

[0014] Furthermore, the hydrogen release control method further comprises:

[0015] Based on the relationship between the equilibrium pressure, hydrogen content and temperature of the solid-state hydrogen storage and supply material, the preset pressure value is set as the equilibrium pressure, the current hydrogen content value is set as the hydrogen content, and the corresponding temperature value is calculated as the hydrogen release temperature. Further, the relationship between the equilibrium pressure, hydrogen content and temperature is calculated by the inverse function of the equilibrium pressure equation of the solid-state hydrogen storage and supply material.

[0016] Furthermore, the relationship among the equilibrium pressure, hydrogen content and temperature is obtained through the equilibrium pressure curve of the solid-state hydrogen storage and supply material.

[0017] Furthermore, the relationship between the equilibrium pressure, hydrogen content and temperature is pre-stored equilibrium pressure data.

[0018] Furthermore, the step of obtaining the balance database includes:

[0019] A reference temperature and enthalpy change value are selected, and a first equilibrium pressure equation of the solid-state hydrogen storage and supply material is constructed using the hydrogen decomposition equilibrium curve of the solid-state hydrogen storage and supply material at the reference temperature. The equilibrium pressure data is calculated based on the hydrogen decomposition equilibrium pressure equation.

[0020] Furthermore, a step function is introduced into the first equilibrium pressure equation to construct a second equilibrium pressure equation.

[0021] The present invention also provides a method for controlling hydrogen release in a solid-state hydrogen storage and supply, comprising:

[0022] Receiving a hydrogen release instruction;

[0023] Detect the current pressure and current temperature of the solid-state hydrogen storage and supply system;

[0024] Comparing the current pressure with a preset pressure value to determine whether the temperature of the solid-state hydrogen storage and supply system needs to be adjusted;

[0025] When the current pressure is less than or equal to the preset pressure value, starting temperature adjustment;

[0026] Wherein, the temperature adjustment includes: determining the dehydrogenation temperature corresponding to the current hydrogen content value and the preset pressure value, and calculating the adjustment temperature according to the dehydrogenation temperature and the current temperature;

[0027] The temperature of the solid-state hydrogen storage and supply system is adjusted to the adjustment temperature.

[0028] Furthermore, the hydrogen release control method further comprises:

[0029] When the solid-state hydrogen storage and supply system receives the instruction to stop releasing hydrogen, it stops releasing hydrogen and stops the temperature adjustment.

[0030] Furthermore, the hydrogen release control method further comprises:

[0031] The regulated temperature is controlled within a predetermined error range within a predetermined time, and the regulated temperature is maintained until a new regulated temperature is changed or the temperature regulation is stopped.

[0032] Furthermore, when calculating the adjustment temperature, the adjustment temperature is corrected according to the temperature difference of the current temperature.

[0033] The present invention also provides a solid-state hydrogen storage and supply system, comprising:

[0034] At least one hydrogen storage bottle, used to contain solid hydrogen storage and supply materials;

[0035] A temperature regulating device, connected to the hydrogen storage bottle and used to regulate the temperature;

[0036] A temperature detection device, installed in the hydrogen storage bottle, for detecting the current temperature;

[0037] A pipeline, used to connect the hydrogen storage bottle to a hydrogen using system;

[0038] A pressure detection device, used for detecting current pressure;

[0039] A switch component, arranged on the pipeline, for controlling the switch of the pipeline;

[0040] The control device is respectively connected to the temperature regulating device, the temperature detecting device, the pressure detecting device and the switch component, and is configured to: receive the current temperature and the current pressure, and determine the dehydrogenation temperature corresponding to the current hydrogen content value and the preset pressure value, and calculate the adjustment temperature according to the dehydrogenation temperature and the current temperature, and control the temperature regulating device to adjust the temperature to the adjustment temperature, and control the switch of the switch component.

[0041] Furthermore, the temperature regulating device is an electric heating device.

[0042] Furthermore, the solid-state hydrogen storage and supply system includes a metal sleeve, one end of which is inserted into the hydrogen storage bottle, and the other end extends out of the hydrogen storage bottle. The electric heating device is an electric heating rod, which is inserted into the metal sleeve, and the temperature detection device is arranged on the electric heating rod.

[0043] Furthermore, the electric heating rod is welded to the metal sleeve, or the electric heating rod is connected to the metal sleeve via a thread.

[0044] Furthermore, the electric heating device is an electric heating sleeve wrapped around the outside of the hydrogen storage bottle, and the temperature detection device is arranged between the electric heating sleeve and the bottle body of the hydrogen storage bottle.

[0045] Furthermore, the control device includes a data interface unit, a calculation unit and a control unit, the data interface unit is connected to the temperature detection device and the pressure detection device to obtain detection data, the calculation unit is used to calculate the adjustment temperature, and the control unit is used to control the temperature adjustment device and the switch component.

[0046] The present invention provides a room-temperature solid-state hydrogen storage and supply absorption / desorption control system and method that is more adaptable to application scenarios. The temperature and hydrogen content parameters of the hydrogen storage and supply materials in the hydrogen cylinder of each hydrogen storage and supply branch in the hydrogen storage and supply system are detected in real time. In the hydrogen storage and supply temperature control system, the relationship between the equilibrium pressure, hydrogen content and temperature of the hydrogen storage and supply materials is used to calculate in real time the current hydrogen content in each branch and the corresponding current temperature. The temperature rise to which the equilibrium pressure can reach a set pressure value that meets the requirements of the hydrogen use system is calculated, and then the hydrogen storage and supply system is adjusted according to the calculated temperature to achieve stable hydrogen absorption / desorption, and refined hydrogen desorption management of the branches of the hydrogen storage and supply system is achieved, thereby improving the complex management of different types of hydrogen storage and supply materials that may exist in the hydrogen storage and supply system.

[0047] The present invention further improves the equilibrium pressure equation for obtaining the adjustment temperature in the hydrogen release control system and applies the improved equilibrium pressure equation to the hydrogen release control system. In the prior art, a setting device is used to obtain the equilibrium pressure equation of each hydrogen storage and supply material. Due to the limitation of the test accuracy, it is impossible to obtain denser data points in the equilibrium pressure equation curve. In actual application scenarios, there may be temperature parameters between the equilibrium pressure equation curves, or when the hydrogen storage and supply material has two hydrogen release platform curves, there may be a blank step data blank area between the two hydrogen release platform curves, and the corresponding adjustment temperature parameters under the equilibrium pressure cannot be obtained, resulting in instability of hydrogen absorption / desorption. In the invention, a step function module is introduced into the equilibrium pressure equation. When obtaining real-time temperature parameters that do not exist between the equilibrium pressure equation curves, the step function module and the existing equilibrium pressure equation are used for fitting calculation to obtain high-precision equilibrium pressure data fitting in the sparse area of ​​the existing equilibrium pressure equation. The equilibrium pressure equation parameters under real-time calculation are provided through data fitting rather than measurement, and accurate and continuous corresponding data of equilibrium pressure, temperature, and hydrogen content are obtained, so as to realize more stable hydrogen absorption / desorption management, contribute to the effective temperature control of the hydrogen storage and supply system, and realize stable and rapid hydrogen supply of the hydrogen storage and supply system. At the same time, the application of medium and low pressure hydrogen storage alloys avoids the risk of system overpressure at ambient temperature. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] Figure 1 is a schematic diagram of a balanced pressure curve of the present invention;

[0049] Figure 2 It is a schematic diagram of a balanced pressure curve with double platforms of the present invention;

[0050] Figure 3 It is a structural schematic diagram of a solid-state hydrogen storage and supply system according to a preferred embodiment of the present invention;

[0051] Figure 4 It is a schematic diagram of the structure of the control device;

[0052] Figure 5 It is a schematic diagram of the structure in which the temperature regulating device is an electric heating rod;

[0053] Figure 6 It is a schematic diagram of the structure in which the electric heating rod is connected by threads;

[0054] Figure 7 It is a schematic diagram of the structure in which the temperature regulating device is an electric heating jacket;

[0055] Figure 8 It is a working flow chart of a preferred embodiment of the solid-state hydrogen storage and supply system of the present invention. DETAILED DESCRIPTION

[0056] The following describes several preferred embodiments of the present invention with reference to the drawings in the specification, so that the technical content is clearer and easier to understand. The present invention can be embodied in many different forms of embodiments, and the protection scope of the present invention is not limited to the embodiments mentioned in the text.

[0057] In the drawings, components with the same structure are indicated by the same numerical reference numerals, and components with similar structures or functions are indicated by similar numerical reference numerals. The size and thickness of each component shown in the drawings are arbitrarily shown, and the present invention does not limit the size and thickness of each component. In order to make the illustration clearer, the thickness of the components is appropriately exaggerated in some places in the drawings.

[0058] Solid-state hydrogen storage is a hydrogen storage technology based on solid-state hydrogen storage materials. The hydrogen release rate of solid-state hydrogen storage materials decreases significantly as the temperature and hydrogen content decrease. However, if the temperature is increased, the hydrogen pressure may exceed the critical value, resulting in excessive pressure in the hydrogen storage and supply system. The use of solid-state hydrogen storage materials with a lower equilibrium pressure can reduce the safety hazard of excessive pressure caused by temperature increase, and can be used at room temperature with better environmental applicability, but may lead to insufficient hydrogen release rate and fail to meet the requirements of the hydrogen use system. The present invention provides a hydrogen release control method for a solid-state hydrogen storage and supply system, which utilizes the hydrogen release equilibrium pressure curve of the solid-state hydrogen storage material, combined with the temperature and pressure of the solid-state hydrogen storage and supply system, controls the temperature of the temperature regulating device to control the hydrogen release temperature and pressure of the solid-state hydrogen storage and supply system, and realizes controllable hydrogen release of the solid-state hydrogen storage and supply system, which can both ensure safety and meet the needs of the hydrogen use system. The hydrogen release control method provided by the present invention can be used in a room temperature solid-state hydrogen storage and supply system, for example, a system using a solid-state hydrogen storage material with a lower equilibrium pressure.

[0059] For a specific hydrogen storage and supply system, it is known how much system pressure is needed to maintain the maximum hydrogen supply flow. Therefore, the pressure value of the hydrogen storage and supply system that meets the requirements of the hydrogen system can be obtained. The pressure value in the hydrogen storage and supply system is a fast-responding measurable variable that can be measured by a corresponding pressure detection device. On this basis, combined with the hydrogen desorption equilibrium pressure curve of the solid hydrogen storage material, the required heating temperature of the hydrogen storage and supply system is deduced through the equilibrium pressure at different temperatures and hydrogen content values, and the temperature rise to what degree under the current hydrogen content can make the equilibrium pressure reach the set system pressure value, thereby maintaining the pressure and hydrogen desorption rate of the hydrogen storage and supply system and achieving controllable hydrogen desorption.

[0060] The hydrogen desorption control method provided by the present invention is described in detail below, and includes the following steps: obtaining the current pressure and current temperature of the solid-state hydrogen storage and supply system; determining the hydrogen desorption temperature corresponding to the current HM (hydrogen content) value and the preset pressure value, and calculating the adjustment temperature according to the hydrogen desorption temperature and the current temperature; and controlling the temperature adjustment device to adjust the temperature to the adjustment temperature.

[0061] Obtaining the current pressure and current temperature of the solid-state hydrogen storage and supply system: This can be achieved by installing a pressure detection device and a temperature detection device in the solid-state hydrogen storage and supply system. For example, the pressure detection device can use a pressure sensor to detect the current hydrogen pressure value. The temperature detection device can use a temperature sensor such as a thermocouple or a thermal resistor.

[0062] Determine the dehydrogenation temperature corresponding to the current HM value and the preset pressure value, and calculate the adjustment temperature based on the dehydrogenation temperature and the current temperature: using the relationship between the equilibrium pressure, hydrogen content and temperature of the solid hydrogen storage material, let the preset pressure value be the equilibrium pressure and the current hydrogen content value be the hydrogen content, and calculate the temperature rise to what degree under the current hydrogen content to make the equilibrium pressure reach the preset pressure value of the system. When the current pressure value is greater than the set preset pressure value, there is no need to increase the temperature to increase the dehydrogenation rate, otherwise the system pressure may be too high, posing a greater safety risk. In other words, the dehydrogenation temperature needs to be lowered at this time. The way to lower the temperature can be to let the temperature of the solid-state hydrogen storage and supply system drop naturally without any intervention, or to take cooling measures to lower the temperature. When the current pressure is less than or equal to the set system pressure value, it indicates that the dehydrogenation rate needs to be intervened, and the dehydrogenation rate needs to be increased by increasing the temperature so that the hydrogen pressure value reaches the set system pressure value.

[0063] The relationship between the equilibrium pressure, hydrogen content and temperature of the solid hydrogen storage material can be reflected by the following methods: equilibrium pressure equation, equilibrium pressure curve, equilibrium pressure database, etc. It should be understood that the relationship is not limited to the above three methods, and other methods that can reflect the relationship between the three can also be applied in the present invention.

[0064] For example, when the equilibrium pressure equation is used, the average hydrogen content of the solid hydrogen storage material is used as the input value, and the required hydrogen desorption temperature can be obtained by direct calculation using the inverse function of the equilibrium pressure equation.

[0065] For example, using a balanced pressure curve, such as Figure 1 As shown, the equilibrium pressure curve is specifically a temperature output mapping function, and the coordinate system of the curve is preferably a horizontal coordinate of the hydrogen content value (HM), and a vertical coordinate of the hydrogen pressure value (P), and different equilibrium pressure curves (T1, T2, T3) are provided at different temperatures T. In some embodiments, the horizontal coordinate may be a temperature value (T), and the vertical coordinate may be a hydrogen pressure value (P), and different equilibrium pressure curves (HM1, HM2, HM3) are provided at different temperature hydrogen content values.

[0066] For example, a balanced pressure database is used, and a more densely populated fitting data point is generated by using the balanced pressure equation and saved.

[0067] The known measured hydrogen desorption equilibrium pressure curve (PCT curve) is mainly obtained by testing the sample material under the measurement device, which has certain application limitations: the data points in the curve have non-measurement point areas, which is not conducive to accurately determining the equilibrium pressure, and the increase in the test point density will affect the test accuracy. With the continuous development of hydrogen storage materials, even double reaction platform curves (such as Figure 2 There is also a non-measurement point area between the two hydrogen release platforms, and the hydrogen release control is more unstable. Figure 2 The diagram shows the measurement point area and non-measurement point area of ​​the hydrogen desorption equilibrium pressure curve (PCT curve), and a schematic diagram of one of the equilibrium pressure curves under the dual reaction platform.

[0068] The numerical point fitting of the unknown measurement area between the equilibrium pressure curves at different temperatures has the first equilibrium pressure equation, which is:

[0069] Determine the reference temperature value T of a known measured equilibrium pressure curve from the current temperature value ref , the known measured equilibrium pressure curve at the reference temperature T ref There is a functional relationship f ref (HM), f ref (HM) is the functional relationship between the hydrogen desorption equilibrium pressure at the reference temperature and HM, and the adjustment temperature T is obtained by the first equilibrium pressure equation;

[0070]

[0071] P eq (T,HM) is the equilibrium pressure corresponding to the adjusted temperature T (that is, the equilibrium pressure that needs to be reached after heating to the adjusted temperature T, that is, reaching the preset pressure), ΔH is the hydrogen desorption enthalpy change value corresponding to the reaction platform (corresponding to the single hydrogen desorption platform), and R is the gas constant.

[0072] As the numerical point fitting of the unknown measurement area between the equilibrium pressure curves between the two hydrogen release platforms in the present invention, there is a second equilibrium pressure equation, specifically:

[0073]

[0074] Determine the reference temperature value T of a known measured equilibrium pressure curve ref , the known measured equilibrium pressure curve at the reference temperature T ref There is a functional relationship f ref (HM), determining a step function value for implementing an approximation of an unknown measurement region to determine a weight parameter in a second equilibrium pressure equation, and obtaining a regulating temperature T from the second equilibrium pressure equation;

[0075] For the above-mentioned second equilibrium pressure equation, in addition to introducing the equilibrium pressure curve between temperatures, weight parameters for approximating different hydrogen desorption reaction platform regions are also introduced, so that the second equilibrium pressure equation can be adapted to data fitting of non-known measurement regions of single reaction platform and double reaction platform hydrogen storage materials.

[0076] Among them, P eq (T,HM) is the equilibrium pressure corresponding to the temperature T and the hydrogen content HM, T ref is the reference temperature, ΔH1 and ΔH2 are the enthalpy changes of hydrogen release corresponding to the first and second reaction platforms (corresponding to the double reaction platform);

[0077] The step function step(x) is a step function that obtains the fitting point of the unknown measurement area close to the known measurement area, passing through the HM in the transition zone between the two reaction platforms. c The difference between the hydrogen content HM measured at the point and in real time is calculated. When the difference between the two is not large, it means that the current measurement value is close to the transition zone. At this time, the hydrogen content HM is located in the middle of the transition zone between the two reaction platforms. In order to fit the second equilibrium pressure equation, the weight value distribution of the two reaction platforms needs to be considered. The step function step(x) value increases from 0 to 1, where the specific value of 0 to 1 is related to HM. c The value weight ratio of the point is related (for example, HM in the middle of the transition zone c In an implementation method of the point, step(x)=0.5), the step function is substituted into the second equilibrium pressure equation for solution; when the difference between the two is large, the difference between the two can be used to determine whether it is approaching the first reaction platform (for example, corresponding to x much greater than 0) or approaching the second reaction platform (for example, corresponding to x much less than 0), thereby obtaining the value of the step function step(x). In one specific implementation method, the step function step(x) is:

[0078]

[0079] HM c is the reference temperature T ref The hydrogen content corresponding to the midpoint of the transition zone of the first and second reaction platforms. If there is only one reaction platform, it is the enthalpy change value corresponding to the midpoint of the platform. ΔH1 and ΔH2 are the same, and R is the gas constant. A good fitting result can be obtained when the size of the transition zone is within the range of 0.001 to 8.

[0080] Preferably, the data reference points of the non-known measurement area have been calculated and fitted by the first equilibrium pressure equation and the second equilibrium pressure equation, and the corresponding adjustment temperature can be obtained by directly querying the data through the preset pressure and the current hydrogen content. As a further embodiment, the HM value collected under actual operation, the real-time temperature value under actual operation and the temperature value obtained by fitting form the data supplement of the non-known measurement area, so as to make the adjustment temperature mapping with denser known points more suitable for actual simulation conditions.

[0081] Control the temperature regulating device to adjust the temperature to the adjustment temperature: After determining the adjustment temperature, the temperature regulating device can be controlled to adjust the temperature. If cooling is required, the temperature regulating device can be uncontrolled without taking cooling measures; if cooling measures are taken, the temperature can be cooled by liquid cooling or air cooling. If the temperature needs to be increased, a heating device, such as an electric heating device, can be selected to increase the temperature by controlling the electric heating device. The electric heating device can be controlled by any method known in the prior art, such as PID control, fuzzy control, etc.

[0082] In some embodiments, since the temperature detection device is arranged at different positions, a temperature difference may occur. Therefore, the adjustment temperature needs to be corrected. For example, the temperature difference T is set according to the different positions of the temperature detection device. d , using T h =T cal +T d Calculate the regulating temperature T of the hydrogen storage and supply system h , where T cal Indicates the hydrogen release temperature. Then adjust the temperature according to the corrected adjustment temperature.

[0083] The present invention also provides a solid-state hydrogen storage and supply system using the above hydrogen release control method, such as Figure 3As shown, it includes a hydrogen storage bottle 1, a temperature regulating device 2, a temperature detecting device 3, a pressure detecting device 4, a pipeline 6, a switch component 5 and a control device. A solid hydrogen storage material is arranged in the hydrogen storage bottle 1, and the hydrogen storage bottle 1 is connected to the temperature regulating device 2, and the temperature regulating device 2 can adjust the temperature in the hydrogen storage bottle 1; the outlet of the hydrogen storage bottle 1 is connected to one end of the pipeline 6, and the other end of the pipeline 6 is connected to the hydrogen use system; the switch component 5 is arranged on the pipeline 6, and is used to control the opening and closing of the pipeline 6 to realize hydrogen discharge or stop hydrogen discharge. The temperature detecting device 3 can be installed at a suitable position in the hydrogen storage bottle 1, and is used to detect the current temperature in the hydrogen storage bottle 1. The pressure detecting device 4 can be installed in the hydrogen storage bottle 1, or installed on the pipeline 6, and is used to detect the current hydrogen pressure value in real time. The control device is communicatively connected with the temperature regulating device 2, the temperature detecting device 3, the pressure detecting device 4 and the switch component 5, and is used for receiving data collected by the temperature detecting device 3 and the pressure detecting device 4, and determining the regulating temperature according to the relationship between the equilibrium pressure, the hydrogen content and the temperature, and then controlling the temperature regulating device 2 to regulate the temperature, and controlling the switch component 5 to open and close.

[0084] The hydrogen storage bottle 1 can be made of materials such as stainless steel and aluminum alloy. It should be understood that the material of the hydrogen storage bottle 1 does not constitute a limitation on the present invention, and all materials for the hydrogen storage bottle 1 known in the prior art can be applied. The number of hydrogen storage bottles 1 can be set to one or more according to actual needs, and the number of hydrogen storage bottles 1 does not constitute a limitation on the present invention. If multiple hydrogen storage bottles 1 are provided, the multiple hydrogen storage bottles 1 are connected in series through a pipeline 6, and the outlet of the pipeline 6 is connected to the hydrogen system.

[0085] The temperature detection device 3 may be a temperature sensor, and any temperature sensor known in the prior art may be applicable to the present invention.

[0086] The pressure detection device 4 may be a pressure sensor or a pressure gauge, and any known pressure sensor or pressure gauge may be applicable to the present invention.

[0087] The components of the control device are as follows: Figure 4As shown, it includes at least one data interface unit, a calculation unit and a control unit. The data interface unit is used to obtain at least one working parameter information of at least one hydrogen storage and supply pipeline 6, such as the current temperature and the current pressure; the calculation unit is used to determine the adjustment temperature according to the relationship between the equilibrium pressure, hydrogen content and temperature of the solid hydrogen storage material; the control unit is used to control the temperature adjustment device 2 to reach the adjustment temperature, and control the opening and closing of the switch component 5. It should be understood that the current hydrogen content value of the hydrogen storage system should be collected or calculated by the existing technology, and used to control the hydrogen release temperature calculation of the device. Among them, the calculation unit can determine the adjustment temperature according to any one or more of the equilibrium pressure equation, equilibrium pressure curve, and equilibrium pressure database. For example, the equilibrium pressure equation is preset in the calculation unit, and the inverse function of the equilibrium pressure equation is used for calculation according to the collected working parameter information; or the equilibrium pressure curve is preset in the calculation unit, and data fitting is performed according to the collected working parameter information to determine the adjustment temperature; or the equilibrium pressure database is stored in the calculation unit, and then data mapping is performed according to the collected information to determine the adjustment temperature. The control device can be integrated into one, that is, each unit is integrated into one circuit device; or a split setting can be adopted, with each unit arranged independently and then communicated with each other.

[0088] The temperature regulating device 2 is preferably an electric heating method. In some embodiments, Figure 5 As shown, an electric heating rod is used for heating, and an opening is provided at one end of the hydrogen storage bottle 1. One end of the metal sleeve 8 is inserted into the hydrogen storage bottle 1 through the opening, and the other end is extended outside the hydrogen storage bottle 1. The opening is sealed to fix the metal sleeve 8 and ensure the sealing of the hydrogen storage bottle 1. The metal sleeve 8 is a hollow pipe inside, and the electric heating rod is inserted into the metal sleeve 8. After the electric heating rod is inserted into the metal sleeve 8, the electric heating rod can be fixed in the metal sleeve 8 by welding. If there are multiple hydrogen storage bottles 1, a metal sleeve 8 is provided in each hydrogen storage bottle 1. The temperature detection device 3 is provided on the electric heating rod. In some embodiments, such as Figure 6 As shown, the end of the metal sleeve 8 for inserting the electric heating rod is provided with a thread, and the electric heating rod is inserted into the metal sleeve 8 and then connected with the thread of the metal sleeve 8 to be fixed.

[0089] In some embodiments, Figure 7 As shown, an electric heating jacket is selected for heating. The electric heating jacket is coated on the outer wall of the hydrogen storage bottle 1, and the temperature detection device 3 is arranged between the electric heating jacket and the bottle body 7 of the hydrogen storage bottle 1.

[0090] It should be understood that the connection method between the temperature regulating device 2 and the hydrogen storage bottle 1 is not limited to the above embodiment. The essence is that a suitable temperature regulating device 2 is selected and installed on the hydrogen storage bottle 1 to achieve temperature regulation, which can be applied in the present invention.

[0091] The switch component 5 is preferably a valve, which can have two modes: manual control and automatic control. The valve can be any valve known in the prior art for the hydrogen pipeline 6.

[0092] The solid-state hydrogen storage and supply system provided by the present invention has the following working process: Figure 8 As shown, it may include:

[0093] Receiving a hydrogen release instruction, opening the switch component 5, and starting hydrogen release;

[0094] Detect the current pressure and current temperature, and determine whether the temperature needs to be adjusted based on the current pressure. If the pressure is greater than the preset value, the current temperature will not be increased; if the pressure is less than or equal to the preset value, the temperature adjustment will be started. Among them, real-time detection can be used to obtain the current pressure; the current pressure and current temperature can also be collected at preset intervals.

[0095] By using the relationship between equilibrium pressure, hydrogen content and temperature, the dehydrogenation temperature corresponding to the current HM value and the preset pressure is determined, and the temperature is adjusted. At this time, in order to further optimize the adjustment temperature, correction can be made according to the temperature difference caused by the different positions of the temperature detection device 3.

[0096] Controlling the temperature adjustment device 2 to adjust the temperature;

[0097] When receiving a command to stop hydrogen discharge at any time, the solid-state hydrogen storage and supply system can be configured to close the switch component 5, stop hydrogen discharge, and stop temperature regulation at the same time.

[0098] After the temperature adjustment device 2 starts to adjust the temperature, it can use continuous heating to make the temperature change continuously, or it can control the temperature within a reasonable error range within a predetermined time and maintain the temperature until a new adjustment temperature is changed or the adjustment is stopped.

[0099] The technical concept of the present invention will be further described below through multiple embodiments.

[0100] Embodiment 1:

[0101] In this embodiment, the rare earth LaNi5 type hydrogen storage alloy is used as the hydrogen storage material, which is loaded into three 1.4L hydrogen storage bottles 1, and together with the temperature adjustment device 2, the temperature detection device 3, the pressure detection device 4, the switch component 5 and the pipeline 6, a room temperature solid-state hydrogen storage and supply system is formed. Figure 3 As shown, a metal sleeve 8 is welded at one end of the hydrogen storage bottle 1 and sealed at the other end, and the temperature regulating device 2 is an electric heating rod inserted into the metal sleeve 8 of the hydrogen storage bottle 1. The temperature detection device 3 is located inside the electric heating rod. The pressure detection device 4 is located in the pipeline 6 to detect the pressure of the pipeline 6 and the hydrogen storage bottle 1 in the hydrogen storage and supply system in real time.

[0102] The rare earth LaNi5 type hydrogen storage alloy has only one hydrogen release reaction platform (HM c =0.65), the dehydrogenation enthalpy change ΔH1 and ΔH2 have the same value and are 28 kJ / mol H2, and taking 25°C as the reference temperature, the dehydrogenation equilibrium pressure curve at 25°C is used to construct the dehydrogenation reaction equilibrium pressure equation of the material. The transition zone size of the step function step(x) is 0.1. The dehydrogenation equilibrium pressure database of the material (i.e., the relationship between equilibrium pressure, temperature, and hydrogen content) is calculated according to the dehydrogenation reaction equilibrium pressure equation. Based on the dehydrogenation equilibrium pressure database, combined with the temperature and pressure values ​​detected by the temperature detection device 3 and the pressure detection device 4, the electric heating device is controlled to control the dehydrogenation temperature and pressure of the hydrogen storage and supply system, so as to realize the controllable dehydrogenation of the room temperature solid-state hydrogen storage and supply system.

[0103] The hydrogen release control process of the solid-state hydrogen storage and supply system is as follows:

[0104] Step 1: If a hydrogen release command is received, open the switch component 5, start hydrogen release, and proceed to step 2; if a hydrogen release stop command is received, stop closing the switch component 5, stop hydrogen release and the heating process of the electric heating rod, and the hydrogen release process stops.

[0105] Step 2: Every 10 seconds, determine whether heating is required based on the pressure P of the hydrogen storage and supply system. If the pressure P>0.6MPa (P d =0.15MPa, a=0.45MPa, P d is the fuel cell operating pressure, a is the correction pressure, and the sum of the two is the preset pressure), then stop heating; if the pressure P≤0.6MPa, start heating and go to step 3.

[0106] Step 3: Use the hydrogen desorption equilibrium pressure database to determine the current HM value and the material desorption temperature (T cal ), combined with the temperature difference caused by the different locations of the temperature detection device 3 of the hydrogen storage and supply system (T d =10℃) and use the formula T h =T cal +10℃Calculate the heating temperature T of the hydrogen storage and supply system h .

[0107] Step 4: Set the heating temperature of the electric heating rod to T h , and turn on the power for heating; re-enter step 1.

[0108] When an emergency instruction to stop hydrogen discharge is received at any time, the switch component 5 is immediately closed to stop the hydrogen discharge and the heating process of the temperature adjustment device 2.

[0109] After the temperature adjustment device 2 starts heating, the temperature is controlled at T h±5℃, and maintain this temperature until T is changed h value or stop heating.

[0110] Example 2

[0111] This embodiment uses a rare earth A2B7 type La-Y-Ni hydrogen storage alloy as a hydrogen storage material, which is loaded into a 1L stainless steel hydrogen storage bottle 1, and together with a temperature regulating device 2, a temperature detecting device 3, a pressure detecting device 4, a switch component 5 and a pipeline 6, constitutes a room temperature solid-state hydrogen storage and supply system. The temperature regulating device 2 is an electric heating rod, which is fixed to the stainless steel hydrogen storage bottle 1 by a threaded connection. The temperature detecting device 3 is located inside the electric heating rod. The pressure detecting device 4 is located in the pipeline 6, and detects the pressure of the pipeline 6 and the hydrogen storage bottle 1 in the hydrogen storage and supply system in real time.

[0112] There are two hydrogen desorption platforms in rare earth A2B7 La-Y-Ni hydrogen storage alloys (HM c =0.7), the dehydrogenation enthalpy change ΔH1 and ΔH2 values ​​of the first and second dehydrogenation platforms are 28.3 kJ / mol H2 and 32.2 kJ / mol H2, respectively, and taking 40°C as the reference temperature, the dehydrogenation equilibrium pressure curve at 40°C is used to construct the dehydrogenation reaction equilibrium pressure equation of the material. The transition zone size of the step function step(x) is 0.25. The dehydrogenation equilibrium pressure database of the material (i.e., the relationship between equilibrium pressure, temperature, and hydrogen content) is calculated according to the dehydrogenation reaction equilibrium pressure equation. Based on the dehydrogenation equilibrium pressure database, combined with the temperature and pressure values ​​detected by the temperature detection device 3 and the pressure detection device 4, the electric heating device is controlled to control the dehydrogenation temperature and pressure of the hydrogen storage and supply system, so as to realize the controllable dehydrogenation of the solid-state hydrogen storage and supply system at room temperature.

[0113] The hydrogen release control process of the solid-state hydrogen storage and supply system is as follows:

[0114] Step 1: If a hydrogen release command is received, open the switch component 5, start hydrogen release, and proceed to step 2; if a hydrogen release stop command is received, stop closing the switch component 5, stop hydrogen release and the heating process of the temperature adjustment device 2, and the hydrogen release process stops.

[0115] Step 2: Every 10 seconds, determine whether heating is required based on the pressure P of the hydrogen storage and supply system. If the pressure P>0.4MPa (P d =0.15MPa, a=0.25MPa), stop heating; if pressure P≤0.4MPa, start heating and go to step 3.

[0116] Step 3: Use the hydrogen desorption equilibrium pressure database to determine the current HM value and the material desorption temperature (T cal ), combined with the temperature difference caused by the different locations of the temperature detection device 3 of the hydrogen storage and supply system (Td =10℃) and use the formula T h =T cal +10℃Calculate the heating temperature T of the hydrogen storage and supply system h .

[0117] Step 4: Set the set heating temperature of the temperature adjustment device 2 to T h , and turn on the power for heating; re-enter step 1.

[0118] When an emergency instruction to stop hydrogen discharge is received at any time, the switch component 5 is immediately closed to stop the hydrogen discharge and the heating process of the temperature adjustment device 2.

[0119] After the temperature adjustment device 2 starts heating, the temperature is controlled at T h ±5℃, and maintain this temperature until T is changed h value or stop heating.

[0120] Example 3

[0121] This embodiment uses titanium AB2 type Ti-Mn-Cr-Zr hydrogen storage alloy as the hydrogen storage material, which is loaded into two 2L aluminum alloy hydrogen storage bottles 1, and together with the temperature regulating device 2, the temperature detection device 3, the pressure detection device 4, the switch component 5 and the pipeline 6, constitute a room temperature solid-state hydrogen storage and supply system. The temperature regulating device 2 is an electric heating sleeve that tightly covers the outer wall of the aluminum alloy hydrogen storage bottle 1. The temperature detection device 3 is located in the middle of the outer wall of the aluminum alloy hydrogen storage bottle 1. The pressure detection device 4 is located in the pipeline 6 to detect the pressure of the pipeline 6 and the hydrogen storage bottle 1 in the hydrogen storage and supply system in real time.

[0122] The dehydrogenation reaction platform of titanium AB2 type Ti-Mn-Cr-Zr hydrogen storage alloy is only one (HM c =0.95), the dehydrogenation enthalpy change ΔH1 and ΔH2 values ​​are both 23.06 kJ / mol H2, and taking 20°C as the reference temperature, the dehydrogenation equilibrium pressure curve at 20°C is used to construct the dehydrogenation reaction equilibrium pressure equation of the material. The transition zone size of the step function step(x) is 0.05. The dehydrogenation equilibrium pressure database of the material (i.e., the relationship between equilibrium pressure, temperature, and hydrogen content) is calculated according to the dehydrogenation reaction equilibrium pressure equation. Based on the dehydrogenation equilibrium pressure database, combined with the temperature and pressure values ​​detected by the temperature detection device 3 and the pressure detection device 4, the electric heating device is controlled to control the dehydrogenation temperature and pressure of the hydrogen storage and supply system, so as to realize the controllable dehydrogenation of the room temperature solid-state hydrogen storage and supply system.

[0123] The hydrogen release control process of the solid-state hydrogen storage and supply system is as follows:

[0124] Step 1: If a hydrogen release command is received, open the switch component 5, start hydrogen release, and proceed to step 2; if a hydrogen release stop command is received, close the switch component 5 to stop hydrogen release and the heating process of the temperature adjustment device 2, and the hydrogen release process stops.

[0125] Step 2: Every 10 seconds, determine whether heating is required based on the pressure P of the hydrogen storage and supply system. If the pressure P>0.8MPa (P d =0.2MPa, a=0.6MPa), stop heating; if pressure P≤0.8MPa, start heating and go to step 3.

[0126] Step 3: Use the hydrogen desorption equilibrium pressure database to determine the current HM value and the material desorption temperature (T cal ), combined with the temperature difference caused by the different locations of the temperature detection device 3 of the hydrogen storage and supply system (T d =15℃) and use the formula T h =T cal +15℃Calculate the heating temperature T of the hydrogen storage and supply system h .

[0127] Step 4: Set the set heating temperature of the temperature adjustment device 2 to T h , and turn on the power for heating; re-enter step 1.

[0128] When an emergency instruction to stop hydrogen discharge is received at any time, the switch component 5 is immediately closed to stop the hydrogen discharge and the heating process of the temperature adjustment device 2.

[0129] After the temperature adjustment device 2 starts heating, the temperature is controlled at T h ±3℃, and maintain this temperature until T is changed h value or stop heating.

[0130] The preferred specific embodiments of the present invention are described in detail above. It should be understood that ordinary technicians in the field can make many modifications and changes based on the concept of the present invention without creative work. Therefore, all technical solutions that can be obtained by technicians in the technical field based on the concept of the present invention through logical analysis, reasoning or limited experiments on the basis of the prior art should be within the scope of protection determined by the claims.

Claims

1. A method for controlling hydrogen release in a solid-state hydrogen storage and supply, characterized in that: include: Obtain the current pressure and current temperature of the solid-state hydrogen storage and supply system; Determine the dehydrogenation temperature corresponding to the current hydrogen content value and the preset pressure value, and calculate the adjustment temperature according to the dehydrogenation temperature and the current temperature; The temperature of the solid-state hydrogen storage and supply system is adjusted to the adjustment temperature.

2. The hydrogen release control method according to claim 1, characterized in that: The hydrogen release control method further comprises: Before calculating the adjustment temperature, determine whether the temperature of the solid-state hydrogen storage and supply system needs to be adjusted.

3. The hydrogen release control method according to claim 2, characterized in that: The hydrogen release control method further comprises: The current pressure is compared with a preset pressure value. When the current pressure is greater than the preset pressure value, the temperature of the solid-state hydrogen storage and supply system is stopped from being increased. When the current pressure is less than or equal to the preset pressure value, the adjustment temperature is calculated according to the hydrogen release temperature and the current temperature.

4. The hydrogen release control method according to claim 1, characterized in that: The temperature regulating device is controlled to regulate the temperature of the solid-state hydrogen storage and supply system to the regulating temperature.

5. The hydrogen release control method according to claim 1, characterized in that: The hydrogen release control method further comprises: Based on the relationship between the equilibrium pressure, hydrogen content and temperature of the solid-state hydrogen storage and supply material, the preset pressure value is set as the equilibrium pressure, the current hydrogen content value is set as the hydrogen content, and the corresponding temperature value is calculated as the hydrogen release temperature.

6. The hydrogen release control method according to claim 5, characterized in that: The relationship between the equilibrium pressure, hydrogen content and temperature is calculated by the inverse function of the equilibrium pressure equation of the solid-state hydrogen storage and supply material.

7. The hydrogen release control method according to claim 5, characterized in that: The relationship between the equilibrium pressure, hydrogen content and temperature is obtained through the equilibrium pressure curve of the solid-state hydrogen storage and supply material.

8. The hydrogen release control method according to claim 5, characterized in that: The relationship between the equilibrium pressure, hydrogen content and temperature is pre-stored equilibrium pressure data.

9. The hydrogen release control method according to claim 8, characterized in that: The step of obtaining the balance database comprises: A reference temperature and enthalpy change value are selected, and a first equilibrium pressure equation of the solid-state hydrogen storage and supply material is constructed using the hydrogen decomposition equilibrium curve of the solid-state hydrogen storage and supply material at the reference temperature. The equilibrium pressure data is calculated based on the hydrogen decomposition equilibrium pressure equation.

10. The hydrogen release control method according to claim 9, characterized in that: A step function is introduced into the first equilibrium pressure equation to construct a second equilibrium pressure equation.

11. A method for controlling hydrogen release in a solid-state hydrogen storage and supply, characterized in that: include: Receiving a hydrogen release instruction; Detect the current pressure and current temperature of the solid-state hydrogen storage and supply system; Comparing the current pressure with a preset pressure value to determine whether the temperature of the solid-state hydrogen storage and supply system needs to be adjusted; When the current pressure is less than or equal to the preset pressure value, starting temperature adjustment; Wherein, the temperature adjustment includes: determining the dehydrogenation temperature corresponding to the current hydrogen content value and the preset pressure value, and calculating the adjustment temperature according to the dehydrogenation temperature and the current temperature; The temperature of the solid-state hydrogen storage and supply system is adjusted to the adjustment temperature.

12. The hydrogen release control method according to claim 11, characterized in that: The hydrogen release control method further comprises: When the solid-state hydrogen storage and supply system receives the instruction to stop releasing hydrogen, it stops releasing hydrogen and stops the temperature adjustment.

13. The hydrogen release control method according to claim 11, characterized in that: The hydrogen release control method further comprises: The regulated temperature is controlled within a predetermined error range within a predetermined time, and the regulated temperature is maintained until a new regulated temperature is changed or the temperature regulation is stopped.

14. The hydrogen release control method according to claim 11, characterized in that: When calculating the adjustment temperature, the adjustment temperature is corrected according to the temperature difference of the current temperature.

15. A solid-state hydrogen storage and supply system, characterized in that: include: At least one hydrogen storage bottle, used to contain solid hydrogen storage and supply materials; A temperature regulating device, connected to the hydrogen storage bottle and used to regulate the temperature; A temperature detection device, installed in the hydrogen storage bottle, for detecting the current temperature; A pipeline, used to connect the hydrogen storage bottle to a hydrogen using system; A pressure detection device, used to detect the current pressure; A switch component, arranged on the pipeline, for controlling the switch of the pipeline; The control device is respectively connected to the temperature regulating device, the temperature detecting device, the pressure detecting device and the switch component, and is configured to: receive the current temperature and the current pressure, and determine the dehydrogenation temperature corresponding to the current hydrogen content value and the preset pressure value, and calculate the adjustment temperature according to the dehydrogenation temperature and the current temperature, and control the temperature regulating device to adjust the temperature to the adjustment temperature, and control the switch of the switch component.

16. The solid-state hydrogen storage and supply system according to claim 15, characterized in that: The temperature regulating device is an electric heating device.

17. The solid-state hydrogen storage and supply system according to claim 16, characterized in that: The solid-state hydrogen storage and supply system includes a metal sleeve, one end of which is inserted into the hydrogen storage bottle, and the other end extends out of the hydrogen storage bottle. The electric heating device is an electric heating rod, which is inserted into the metal sleeve, and the temperature detection device is arranged on the electric heating rod.

18. The solid-state hydrogen storage and supply system according to claim 17, characterized in that: The electric heating rod is welded to the metal sleeve, or the electric heating rod is connected to the metal sleeve via a thread.

19. The solid-state hydrogen storage and supply system according to claim 16, characterized in that: The electric heating device is an electric heating sleeve covering the outside of the hydrogen storage bottle, and the temperature detection device is arranged between the electric heating sleeve and the bottle body of the hydrogen storage bottle.

20. The solid-state hydrogen storage and supply system according to claim 15, characterized in that: The control device includes a data interface unit, a calculation unit and a control unit. The data interface unit is connected to the temperature detection device and the pressure detection device to obtain detection data. The calculation unit is used to calculate the adjustment temperature. The control unit is used to control the temperature adjustment device and the switch component.

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