Heating cartridge for vehicle use, pre-treatment method and regeneration method for the heating cartridge

Abstract

To enable a heat generation system using a hydrogen storage material, which utilizes a heat generation phenomenon in which output enthalpy becomes higher than input enthalpy, to be mounted on a vehicle.SOLUTION: An on-vehicle heating element cartridge of the invention includes: a hydrogen gas filling container; a heating material including a hydrogen storage material; and a heating part which heats the heat material. The heating material and the heating part are disposed within the filling container. Devices needed for pretreatment and regeneration treatment of the heating material are separated, and these treatments are performed on another device at the outside of a vehicle. Thus, the on-vehicle heating element cartridge can be mounted on the vehicle.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to an in-vehicle heating element cartridge, a pre-treatment method and a regeneration method for the heating element cartridge, and more particularly to an in-vehicle heating element cartridge that utilizes excess heat generated by a hydrogen storage material, and a pre-treatment method and a regeneration method for the heating element cartridge. [Background technology]

[0002] Conventionally, PTC (positive temperature coefficient) heaters with self-temperature control function using semiconductor ceramics have been used for the heated seats of electric vehicles (EVs).

[0003] The resistance value of the PTC heater increases rapidly when the temperature exceeds the Curie temperature. Therefore, at low temperatures, a large current flows and the amount of heat generated increases. The resistance value increases due to the temperature rise caused by heat generation, and the current is limited, preventing unnecessary heat generation and saving energy.

[0004] However, since PTC heaters use electricity as their energy source, their use in electric vehicles significantly reduces their driving range.

[0005] Also known is a heat generation system that uses excess heat, that is, a heat generation phenomenon in which the output enthalpy is greater than the input enthalpy, and that uses a hydrogen storage material (see Patent Document 1).

[0006] If this heating system is used in the heated seats of an electric vehicle, the output enthalpy can be made higher than the input enthalpy, thereby preventing a decrease in driving range. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 2017-110835 Summary of the Invention [Problem to be solved by the invention]

[0008] However, the heat generation system described in Patent Document 1 is equipped with devices for supplying and adjusting the pressure of hydrogen gas and nitrogen gas, and is a complex and large-scale heat generation system, making it unsuitable for use in a vehicle.

[0009] The present invention has been made in consideration of the problems associated with the prior art, and its purpose is to provide an in-vehicle heating element cartridge that utilizes the heat generation phenomenon that generates excess heat, as well as a pre-processing method and a regeneration method for the heating element cartridge. [Means for solving the problem]

[0010] As a result of extensive research into achieving the above-mentioned object, the inventors discovered that the above-mentioned object could be achieved by separating the equipment required for the above-mentioned pretreatment method and regeneration treatment method, and carrying out the pretreatment and regeneration treatment of the heat-generating material in separate equipment outside the vehicle, and by incorporating the heat-generating material required for the heat-generating phenomenon that generates the excess heat and the heating unit that causes the heat-generating phenomenon into a cartridge-type hydrogen gas-filled container, thereby completing the present invention.

[0011] That is, the in-vehicle heating element cartridge of the present invention comprises a hydrogen gas filled container; The heating element includes a heat generating material containing a hydrogen storage material, and a heating unit for heating the heat generating material. The heat generating material and the heating unit are placed in the filling container, The pretreatment and regeneration of the heat generating material are carried out outside the vehicle. It is characterized by:

[0012] The pretreatment method for an on-vehicle heating cartridge of the present invention is a pretreatment method carried out before the on-vehicle heating cartridge is mounted on a vehicle. The method comprises a filling step of filling the hydrogen gas container with hydrogen gas, a pre-heating step of heating the heat generating material, and a cooling step of cooling the heat generating material to room temperature, wherein the pre-heating step maintains the heating temperature within a temperature range in which the heat generating material coexists in two phases, thereby forming a heat generating material in which the two phases coexist.

[0013] Furthermore, the regeneration method for regenerating an on-vehicle heating element cartridge of the present invention is a regeneration method for regenerating the heat generating material of a used on-vehicle heating element cartridge. The method further comprises a regeneration heating step of heating the heat generating material and a cooling step of cooling the heat generating material to room temperature, wherein the regeneration heating step heats the heat generating material to a temperature at which it forms a liquid phase, and then holds the heat generating material in a temperature range where two phases coexist, thereby forming a heat generating material in which two phases coexist. [Effects of the Invention]

[0014] According to the present invention, the devices required for the above pretreatment method and regeneration method are separated, and therefore it is possible to provide an in-vehicle heating element cartridge that can be mounted on a vehicle and utilizes the heat generation phenomenon that generates excess heat, as well as a pretreatment method and regeneration method for the heating element cartridge. [Brief explanation of the drawings]

[0015] [Figure 1] FIG. 2 is a cross-sectional view showing an example of an in-vehicle heating element cartridge. [Figure 2] This is an equilibrium diagram of a Ni-Zr alloy. [Figure 3] This is an equilibrium diagram of an Al-Ni alloy. [Figure 4] This is an equilibrium diagram of an Al-Ca alloy. [Figure 5] FIG. 2 is an X-ray diffraction spectrum diagram of a heat generating material. DETAILED DESCRIPTION OF THE INVENTION

[0016] <In-vehicle heating element cartridge> The vehicle-mounted heating element cartridge of the present invention will now be described in detail. A cross-sectional view of the above-mentioned in-vehicle heating element cartridge is shown in FIG. This on-vehicle heating element cartridge includes a hydrogen gas container, a heating material containing a hydrogen absorbing material, and a heating section for heating the heating material.

[0017] The in-vehicle heating element cartridge supplies hydrogen gas into a hydrogen gas filled container, causes the heat generating material to absorb hydrogen, and then heats the heat generating material to release hydrogen. This hydrogen release reaction is an endothermic reaction, but when the heat generating material releases hydrogen, pulsed heat is generated, and this pulsed heat generates excess heat that exceeds the amount of heat used to heat the heat generating material.

[0018] When two phases coexist in the heat-generating material, the equilibrium point where energy balance is achieved differs between the two phases, and the hydrogen absorption and desorption speeds differ, so one phase releases hydrogen while the other absorbs it. This state continues until the equilibrium point of one phase is reached, at which point hydrogen release from the other phase stops.

[0019] Since the equilibrium point of one phase is shifted from the equilibrium point of the other phase, the other phase releases hydrogen and the one phase absorbs hydrogen, and the release of hydrogen from the other phase continues past the equilibrium point of the one phase and up to the equilibrium point of the other phase.

[0020] As described above, the cycle of hydrogen release from one phase, the equilibrium point of one phase, hydrogen release from the other phase, and the equilibrium point of the other phase is repeated, and the pulsating heat generation can be continuously obtained until the hydrogen storage function of the heat-generating material decreases.

[0021] As described above, since the hydrogen release reaction is an endothermic reaction, the heat generation from the heat generating material can be stopped by stopping the heating by the heating unit, and the heat generation from the heat generating material can be resumed by heating the heat generating material again.

[0022] The exothermic material can be an alloy in which two solid phases coexist under desired conditions. It is preferable to use an alloy in which the difference in enthalpy of formation between the metal hydride forming one phase and the metal hydride forming the other phase is large.

[0023] Examples of alloys in which two solid phases with a large difference in formation enthalpy coexist include Ni-Zr alloys with nickel (Ni):zirconium (Zr) ratios of 30:70 to 40:60 mol%, Al-Ni alloys with aluminum (Al):nickel (Ni) ratios of 75:25 to 65:35 mol%, and Al-Ca alloys with aluminum (Al):calcium (Ca) ratios of 80:20 to 70:3 mol%. Phase diagrams of Ni-Zr alloy, Al-Ni alloy, and Al-Ca alloy are shown in FIGS.

[0024] From Figure 2, for example, in the case of an alloy with Ni:Zr=65:35mol%, Ni 10 It can be seen that multiple solid phases of Zr7 and Ni21Zr8 phases are formed.

[0025] The heating unit that releases hydrogen from the heat generating material may be located anywhere in the hydrogen gas-filled container as long as it can efficiently heat the heat generating material, and may be located in one location or multiple locations, but it is preferable that at least one heating unit is located in the center of the heat generating material. By heating the heat generating material from the center, the heat from the heating unit can be transferred to the heat generating material without escaping to the outside.

[0026] The hydrogen container may have any shape to suit the location where the on-board heating element cartridge is used, but a long, thin cylindrical shape allows for heating over a wide area in the longitudinal direction.Furthermore, if the hydrogen container is cylindrical and the heating section is located on the central axis of the cylinder, the heating material can be heated evenly.

[0027] The heating unit can be any unit capable of heating the exothermic material to a temperature at which it releases hydrogen, but if the pretreatment and regeneration treatment described below are also performed in the heating unit, it must be capable of heating the exothermic material to a temperature at which it becomes liquid. For example, an electric heater using an electric heating wire or the like can be used as such a heating unit.

[0028] To regenerate the heat-generating material, it is necessary to heat it to a temperature at which it forms a liquid phase. By making the heating unit detachable, the regeneration process can be carried out with the heating unit removed, preventing damage to the heating unit during the regeneration process.

[0029] An example of an in-vehicle heating element cartridge with a detachable heating unit is a hydrogen gas filling container with a double-cylinder structure consisting of two cylinders, an inner cylinder and an outer cylinder, with the heating material placed on the outside of the inner cylinder and the heating unit placed on the inside of the inner cylinder.

[0030] With this structure, the heating material in the hydrogen gas container and the heating unit are separated by the inner cylinder, so the heating unit can be easily removed.

[0031] It is also preferable that the hydrogen-filled vessel is provided with a support having a communication hole extending in the longitudinal direction of the vessel. Since the heat generating material is supported by a support body having communicating holes, hydrogen gas can easily pass through the communicating holes and come into contact with the heat generating material, thereby increasing the reaction site between the heat generating material and hydrogen gas and increasing the amount of heat generated.

[0032] In addition, the pretreatment process can shorten the pretreatment time because the exothermic material can easily absorb hydrogen. Furthermore, even if the exothermic material becomes liquid during the regeneration process, the exothermic material can have communicating holes formed therein, preventing the exothermic material from becoming dense and suppressing a decrease in the contact area between the exothermic material and hydrogen gas.

[0033] The support may be a porous support that is permeable to hydrogen gas but not to the liquid phase heat generating material, and examples thereof include ceramic supports.

[0034] The on-vehicle heating element cartridge preferably has a positioning guide that determines the position where it is to be attached to the vehicle. Examples of the positioning guide include a groove or flat surface provided on the hydrogen gas container, which allows the on-vehicle heating element cartridge to be securely attached to the vehicle.

[0035] The in-vehicle heating element cartridge can be installed inside the vehicle, such as in the seat, the instrument panel, the dash panel, the floor, or the roof.

[0036] Furthermore, when the heating material of an in-vehicle heating element cartridge is a Ni-Zr alloy, heating the heating material to approximately 580°C will cause the surface temperature to reach approximately 600°C due to excess heat, so it is preferable to provide insulation at the location where the in-vehicle heating element cartridge is attached or around the in-vehicle heating element cartridge.

[0037] The thermal conductivity of the heat insulating material is preferably 0.001 to 0.003 [W / m·K], and an example of such a heat insulating material is a silica particle-filled vacuum heat insulating material.

[0038] <Pretreatment method> The pretreatment method of the present invention is a treatment carried out using a separate device outside the vehicle before the in-vehicle heating element cartridge is installed in the vehicle, and is a treatment that enables excess heat to be generated from the heating material.

[0039] The pretreatment method includes a filling step of filling a hydrogen gas container with hydrogen gas, a pretreatment heating step, and a cooling step of cooling the heat-generating material to room temperature.

[0040] The filling step is a process of filling a hydrogen gas container with hydrogen gas and causing the heat generating material in the hydrogen gas container to occlude hydrogen, thereby forming a metal hydride.

[0041] The pressure of the hydrogen gas filled into the hydrogen gas container is preferably higher than atmospheric pressure. If the container can withstand this pressure, the higher the hydrogen gas pressure, the larger the diffusion coefficient, and therefore the shorter the time required for pretreatment.

[0042] The pre-treatment heating step is a treatment for converting the exothermic material into a desired composition in which two solid phases coexist, by heating the exothermic material to a temperature range in which the two phases coexist and maintaining that temperature.

[0043] The temperature range in which two solid phases of a heat-generating material coexist varies depending on the alloy that makes up the heat-generating material, but can be determined from its equilibrium phase diagram. For example, in the case of a Ni-Zr alloy, it is about 1000°C.

[0044] The time for which the temperature is maintained within the above range is approximately 10 to 20 hours, although this depends on the type of exothermic material and the pressure of the hydrogen gas.

[0045] After forming a heat-generating material of the desired composition in which two solid phases coexist through the pre-treatment heating step, the material is allowed to cool to room temperature.

[0046] The pretreatment method preferably includes an oxygen removal step before the filling step. By removing oxygen from the hydrogen gas-filled vessel, oxidation of the heat-generating material is prevented, and a heat-generating material in which two solid phases of the desired composition coexist can be formed.

[0047] The oxygen removal step can be carried out by first replacing the gas in the hydrogen gas container with an inert gas such as nitrogen gas, and then evacuating the container.

[0048] <Recycling method> The regeneration method of the present invention is a process for restoring the hydrogen storage function of a heat generating material whose hydrogen storage function has been reduced, thereby enabling it to generate excess heat. The regeneration method is carried out by removing the on-board heating element cartridge from the vehicle and using a separate device outside the vehicle.

[0049] The regeneration method includes a regeneration heating step of heating the heat generating material, and a cooling step of cooling the heat generating material to room temperature.

[0050] The regeneration heating process involves heating the heat generating material to a temperature at which it becomes liquid, converting the heat generating material into a homogeneous single phase, and then cooling it to a temperature range at which two solid phases coexist, and maintaining that temperature to form a heat generating material in which the two phases coexist again.

[0051] The temperature at which the exothermic material becomes liquid and the temperature range in which two solid phases coexist can be determined from the equilibrium diagram. The holding time in the temperature range in which two solid phases coexist is approximately 15 to 25 hours, depending on the type of exothermic material and the pressure of the hydrogen gas.

[0052] At this time, by placing the heat generating material close to the heating part, the heat from the heating part is efficiently transferred to the heat generating material, so that hydrogen can be released and excess heat can be obtained with little energy.

[0053] Then, after a heat-generating material of the desired composition in which two solid phases coexist is formed by the regeneration heating step, the material is allowed to cool to room temperature.

[0054] The regeneration treatment method may, if necessary, have a filling step of filling the hydrogen gas into the hydrogen gas filling vessel before the regeneration heating step. When the hydrogen gas pressure has dropped, the hydrogen gas container can be filled with hydrogen gas again to form a heat-generating material in which two solid phases of the desired composition coexist.

[0055] In addition, in the above-mentioned regeneration method, it is preferable to remove the heating unit from the vehicle-mounted heating element cartridge before the regeneration heating step, and then perform the regeneration heating step to form a heat-generating material of the desired composition in which two solid phases coexist, and then attach the heating unit to the vehicle-mounted heating element cartridge.

[0056] The regeneration heating process heats the heat generating material to a temperature at which it becomes liquid. Therefore, if the regeneration heating process is performed while the heating unit is attached to the vehicle-mounted heating element cartridge, the heating unit may be damaged. However, by removing the heating unit before performing the regeneration heating process, damage to the heating unit can be prevented.

[0057] In addition, if the heating unit can heat the heat generating material to a temperature at which it becomes liquid, the regeneration process may be performed by the heating unit provided in the in-vehicle heating element cartridge without using a separate device outside the vehicle. [Example]

[0058] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0059] A hydrogen gas-filled container had a double-cylinder structure with an inner cylinder of 10 mm diameter inside an outer cylinder of 30 mm diameter and 150 mm length. A ceramic support with communicating holes in the longitudinal direction was inserted between the inner and outer cylinders, and pellets of solidified Zr2Ni powder were filled and held by the support.

[0060] (Pretreatment) After flowing nitrogen gas at 250 mL / min for 10 minutes into the in-vehicle heating element cartridge, 1.0 × 10 2 A vacuum was drawn to a pressure of 1000 Pa. Then, hydrogen gas was introduced at a rate of 3.30 mL / min until the hydrogen partial pressure reached 6.0 × 10 4 The hydrogen gas was filled up to 100 Pa.

[0061] An in-vehicle heating element cartridge filled with hydrogen gas was heated to 1000°C in an electric furnace and held for 15 hours to form a Ni-Zr alloy in which two solid phases coexist.After cooling to room temperature, a rod-shaped electric heater was inserted so that it was in contact with the inner wall of the inner cylinder, and an in-vehicle heating element cartridge was produced.

[0062] The heating material (Ni-Zr alloy) was removed from the pretreated in-vehicle heating element cartridge and analyzed using an X-ray diffraction device, confirming that the Ni-Zr alloy formed two solid phases. Figure 5 shows the diffraction spectrum of the Ni-Zr alloy.

[0063] (using heat) The temperature of the electric heater was set to 580°C to heat the Zr-Ni alloy, generating excess heat. The surface temperature of the in-vehicle heating element cartridge was 600°C, and it was confirmed that excess heat could be obtained.

[0064] (Recycling) After the generation of excess heat had ceased, the rod-shaped electric heater was removed from the on-board heating element cartridge, and the cartridge was heated to 1300°C in an electric furnace to form a liquid phase of Ni-Zr alloy. The temperature was then lowered to 1000°C and held there for 20 hours.

[0065] The heating material (Ni-Zr alloy) was taken out of the regenerated in-vehicle heating element cartridge and analyzed using an X-ray diffractometer. The diffraction spectrum of the Ni-Zr alloy after regeneration was the same as that of the Ni-Zr alloy after pretreatment, confirming the formation of two solid phases.

[0066] When a rod-shaped electric heater was attached to the regenerated in-vehicle heating element cartridge and heated, excess heat was generated, confirming that the regeneration process of the present invention can regenerate the heating material. [Explanation of symbols]

[0067] 1. In-vehicle heating element cartridge 2. Hydrogen gas container 21 Outer cylinder 22 Inner cylinder 3 Heat generating materials 4 Support 41 Communication hole 5 Heating section 6 Hydrogen injection valve 7 Purge valve

Claims

1. a hydrogen gas filling container; a heat-generating material including a hydrogen storage material; a heating unit that heats the heat generating material, the heat generating material and the heating unit are disposed in the filling container, The heating element cartridge for vehicle use is characterized in that the pretreatment and regeneration treatment of the heat generating material are carried out outside the vehicle.

2. The shape of the filling container is cylindrical, 2. The heating cartridge for vehicle use according to claim 1, wherein the heating portion is disposed on the central axis of the cylindrical cartridge.

3. The filling container has a double-cylinder structure consisting of two cylinders, an inner cylinder and an outer cylinder, The heat generating material is disposed on the outside of the inner cylinder, 3. The heating element cartridge for vehicle use according to claim 2, wherein the heating portion is disposed inside the inner cylinder.

4. 4. The heating element cartridge for vehicle use according to claim 1, wherein the filling container has a positioning guide portion.

5. Further, a support for supporting the heat generating material within the filling container is provided, 5. The heating element cartridge for vehicle use according to claim 1, wherein the support body has a communication hole extending in the longitudinal direction of the filling container.

6. A pretreatment method for a heating element cartridge for vehicle installation according to any one of claims 1 to 5 before installation in a vehicle, comprising: a filling step of filling the hydrogen gas filling container with hydrogen gas; a pre-treatment heating step of heating the heat generating material; a cooling step of cooling the heat generating material to room temperature, A pretreatment method for an in-vehicle heating cartridge, characterized in that the pretreatment heating step maintains the heating temperature within a temperature range in which the heat-generating material coexists in two phases, thereby forming a heat-generating material in which two phases coexist.

7. 7. The pretreatment method according to claim 6, wherein the hydrogen filling step is carried out at a filling pressure higher than atmospheric pressure.

8. 8. The pretreatment method for an on-vehicle heating element cartridge according to claim 6, further comprising an oxygen removal step of removing oxygen from the filling vessel before the hydrogen filling step.

9. A regeneration method for regenerating the in-vehicle heating element cartridge according to any one of claims 1 to 5, comprising: a regeneration heating step of heating the heat generating material; a cooling step of cooling the heat generating material to room temperature, A method for regenerating an in-vehicle heating element cartridge, characterized in that the regeneration heating step involves heating the heat generating material to a temperature at which it forms a liquid phase, and then maintaining the heat generating material in a temperature range where two phases coexist to form a heat generating material in which two phases coexist.

10. The method further includes a filling step of filling the hydrogen gas into the hydrogen gas filling container before the regeneration heating step, 10. The method for regenerating an on-vehicle heating element cartridge according to claim 9, wherein the hydrogen filling step is carried out at a filling pressure higher than atmospheric pressure.

11. The method further includes a removing step of removing the heating unit from the in-vehicle heating cartridge before the regenerative heating step, and an attaching step of attaching the heating unit to the in-vehicle heating cartridge after the regenerative heating step, 11. The method for recycling an on-vehicle heating cartridge according to claim 9, wherein the heating step for recycling is a treatment performed by heating the on-vehicle heating cartridge from the outside.

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