CN114122467B - Hydrogen energy power supply device and method for hydrogen supply by hydrolysis of hydrogen storage material and normal low-temperature self-starting - Google Patents
Hydrogen energy power supply device and method for hydrogen supply by hydrolysis of hydrogen storage material and normal low-temperature self-starting Download PDFInfo
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- CN114122467B CN114122467B CN202111250917.3A CN202111250917A CN114122467B CN 114122467 B CN114122467 B CN 114122467B CN 202111250917 A CN202111250917 A CN 202111250917A CN 114122467 B CN114122467 B CN 114122467B
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 238
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 238
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 232
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 49
- 239000011232 storage material Substances 0.000 title claims abstract description 45
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000000446 fuel Substances 0.000 claims abstract description 104
- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
- 239000007789 gas Substances 0.000 claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 238000009530 blood pressure measurement Methods 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims description 54
- 239000000463 material Substances 0.000 claims description 33
- 239000012782 phase change material Substances 0.000 claims description 27
- 239000012295 chemical reaction liquid Substances 0.000 claims description 21
- 238000003860 storage Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000004321 preservation Methods 0.000 claims description 13
- 230000017525 heat dissipation Effects 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 229910012375 magnesium hydride Inorganic materials 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052744 lithium Inorganic materials 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 230000008569 process Effects 0.000 description 5
- 238000009835 boiling Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000007689 inspection Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- RSHAOIXHUHAZPM-UHFFFAOYSA-N magnesium hydride Chemical compound [MgH2] RSHAOIXHUHAZPM-UHFFFAOYSA-N 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/065—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by dissolution of metals or alloys; by dehydriding metallic substances
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04223—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells
- H01M8/04225—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells during start-up
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04223—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells
- H01M8/04268—Heating of fuel cells during the start-up of the fuel cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/0438—Pressure; Ambient pressure; Flow
- H01M8/04388—Pressure; Ambient pressure; Flow of anode reactants at the inlet or inside the fuel cell
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
Abstract
The invention discloses a hydrogen energy power supply device and a power supply method thereof for normal low-temperature self-starting of hydrogen supply by hydrolysis of a hydrogen storage material, wherein the device comprises a hydrolysis hydrogen production unit, a barometric pressure measurement control unit and a fuel cell starting output unit; the hydrogen outlet of the hydrolysis hydrogen production unit is communicated with the gas path hydrogen inlet of the air pressure measurement control unit, and the air inlet of the fuel cell starting output unit is communicated with the gas path output of the air pressure measurement control unit. The whole device does not need external power supply, internal lithium battery power supply and other external energy consumption, and the chemical energy is directly converted into electric energy by the hydrogen fuel cell; the invention can control the reaction of the hydrolysis hydrogen production unit to be carried out and stopped at any time and any place, and the fuel cell starts the output unit hydrogen fuel cell to stop starting; meanwhile, when the hydrogen storage material is used for hydrolysis reaction, a large amount of heat is released, and a detachable heat exchange device is added at low temperature, so that the hydrogen fuel cell can be smoothly started at low temperature. The invention has reasonable scheme, simple structure, easy realization, small volume and weight of the whole device, simple and convenient operation and is applicable to stable operation of different environmental scenes.
Description
Technical Field
The invention belongs to the technical field of power supply devices, and particularly relates to a normal-low-temperature self-starting hydrogen energy power supply device and a power supply method for hydrogen storage material hydrolysis hydrogen supply.
Background
"Hydrogen" is considered one of the most promising clean energy sources in the twentieth century because of its abundance, non-pollution, and renewable properties, combined with its high energy density. The hydrogen fuel cell is used as a device for directly converting chemical energy into electric energy, the power generation is not limited by Carnot cycle, the power generation efficiency can reach 85-90%, the energy conversion efficiency is 2-3 times higher than that of a domestic internal combustion engine, and the device is free of mechanical parts, quiet, noiseless, pollution-free, quick in starting and has good application prospect in the field of portable power sources. The hydrogen fuel power supply has the advantages of quick start, small heat preservation problem, simple structure, high unitization reliability of the module and no pollution in the power generation process; the proton exchange membrane in the hydrogen fuel cell needs a certain humidity when the galvanic pile works, the hydrolysis hydrogen storage material is used as a hydrogen source to supply hydrogen to the fuel cell, the safety is high, the high-pressure transportation and the high-pressure hydrogen release are avoided, the real-time and instant preparation can be realized, and meanwhile, the proton exchange membrane has a certain self-humidifying function.
The prior art [ CN 213483787U 2021.06.18] provides a portable hydrogen energy power supply for individual combat, which is provided with a water tank, an actuating mechanism, a reaction mechanism and a power supply mechanism, wherein the liquid adding operation is required to be performed for a plurality of times, the reaction chamber is divided into a plurality of layers, meanwhile, the structure is more complicated, the added sample is required to be wrapped, and the whole using steps are more complicated.
The prior art [ CN 110265691A 2019.09.20] provides a hydrogen supply integrated system for controllable hydrolysis hydrogen release, which is suitable for a fuel cell, has perfect control part of the whole device, is suitable for hydrogen release of hydrolysis materials, and still has the problems of complex structure, higher cost, large mass and volume, incapability of running at low temperature and the like.
The existing power supply device for the hydrogen fuel cell has single function, cannot control the reaction process, and is inconvenient to use; some of the devices have complex structures, large volume and weight and are inconvenient to operate; some of the energy-saving device has poor adaptability, cannot independently operate in a low-temperature environment, needs auxiliary devices and additional power supply, and has low energy utilization rate. Therefore, the environmental suitability of the hydrogen energy fuel cell is important.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a hydrogen energy power supply device and a power supply method which are capable of being automatically started at a low temperature and are used for supplying hydrogen by hydrolysis of a hydrogen storage material, so as to solve the problem that the current hydrogen fuel cell power supply device cannot control the reaction process; the structure is complex, the volume and the weight are large, and the operation is inconvenient; the environment adaptability is poor, the operation can not be carried out independently in a low-temperature environment, and the technical problems of auxiliary power supply and low energy utilization rate are required.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the invention discloses a hydrogen energy power supply device for normal low-temperature self-starting of hydrogen supply by hydrolysis of a hydrogen storage material, which comprises a hydrolysis hydrogen production unit, a barometric measurement control unit and a fuel cell starting output unit; the hydrogen outlet of the hydrolysis hydrogen production unit is communicated with the gas path hydrogen inlet of the air pressure measurement control unit; an air inlet of the fuel cell starting output unit is communicated with an air channel output port of the air pressure measurement control unit;
The fuel cell starting output unit comprises a hydrogen fuel cell, a load part and a low-temperature starting unit, wherein the low-temperature starting unit is used for starting the hydrogen fuel cell at a low temperature, and a power interface of the hydrogen fuel cell is connected with a load part interface;
the low-temperature starting unit comprises a low-temperature starting device I and a low-temperature starting device II, wherein the hydrogen fuel cell is started through the low-temperature starting device I at the temperature of-10 to 0 ℃, and the hydrogen fuel cell is started through the low-temperature starting device II at the temperature of-40 to-10 ℃.
Further, the low-temperature starting device I comprises a cooling fan and a spiral heating air circuit, the spiral heating air circuit is arranged on the pile surface of the hydrogen fuel cell, and the cooling fan is arranged on the reverse side of the pile surface of the hydrogen fuel cell.
Further, the hydrolysis hydrogen production unit comprises a liquid storage tank and a reaction tank, and the reaction tank is connected with the liquid storage tank through a balance gas circuit; the upper part of the liquid storage tank is connected with a four-way valve through a pipeline, one way of the four-way valve is connected with a liquid inlet control valve, the other way of the four-way valve is connected with a vacuumizing control valve, the other way of the four-way valve is connected with a balance gas circuit, the lower part of the liquid storage tank is connected with a reaction tank through a liquid inlet pipeline, and a reaction liquid control valve capable of controlling the flow rate of liquid is arranged on the liquid inlet pipeline;
The reaction tank is provided with a gas path outlet and a charging port of a hydrogen supply path, and the gas path outlet of the hydrogen supply path is provided with an unloading valve; the reaction tank is internally provided with a hydrogen storage material;
The hydrogen storage material is one of a graphene interface nano valve solid hydrogen storage material, sodium borohydride or magnesium hydride.
Further, the low-temperature starting device II is a detachable heat exchange device arranged outside the reaction tank, and the detachable heat exchange device consists of a phase change material, a heat insulation sheath, a heat conduction layer, a heat transfer connecting pipeline, a heat dissipation area and a material exchange port;
The heat conduction layer, the phase change material, the heat conduction layer and the heat preservation sheath are sequentially arranged outside the reaction tank from inside to outside, the material changing port is arranged on one side of the heat preservation sheath, and the heat dissipation area is arranged in a gap area between the pile surface of the hydrogen fuel cell and the spiral heating gas circuit; the heat transfer connecting pipeline is intersected with the heat dissipation area.
Furthermore, the phase change material is a liquid-gas phase change material or a solid-liquid phase change material, and is added through a material changing port, and the material changing port is provided with a switch valve.
Further, the heat conducting layer is coated outside the phase change material, and adopts a heat conducting silica gel sheet or an alumina ceramic sheet;
in the detachable heat exchange device, heat preservation jackets are added outside the heat conduction layer and outside the heat transfer pipeline, and the heat preservation jackets are made of light plastic or PVC materials.
Further, the air pressure measurement control unit comprises a plurality of control devices, and the plurality of control devices are arranged on a pipeline between the reaction tank and the fuel cell starting output unit;
the control device comprises an unloading valve, a positive pressure gauge, a first control valve, a pressure reducing valve, a second control valve, a positive pressure gauge, a negative pressure gauge and a one-way valve, wherein the positive pressure gauge and the positive pressure gauge are arranged on a hydrogen supply path, the middle of the positive pressure gauge and the positive pressure gauge is divided into two parallel branches, one branch is the pressure reducing valve and the first control valve, the other branch is the second control valve, and the one-way valve is arranged in front of a hydrogen inlet of the hydrogen fuel cell.
Further, the hydrogen fuel cell is a proton exchange membrane fuel cell, and the normal working pressure range of hydrogen at the air inlet of the hydrogen fuel cell is 0.045-0.065 MPa; the load section should be matched to the hydrogen fuel cell power.
The invention also discloses a power supply method of the hydrogen energy power supply device which is automatically started at a low temperature and is used for supplying hydrogen by hydrolysis of the hydrogen storage material, and the power supply method of the hydrogen energy power supply device which is automatically started at a low temperature and is used for supplying hydrogen by hydrolysis of the hydrogen storage material comprises a normal temperature power supply mode above 0 ℃ and a subzero low temperature power supply mode; directly starting the hydrogen fuel cell in a normal temperature power supply mode at the temperature of more than 0 ℃;
Starting in the subzero low-temperature power supply mode is divided into two cases, wherein one case is that the hydrogen fuel cell is started through the low-temperature starting device I at the temperature of-10 to 0 ℃, and the other case is that the hydrogen fuel cell is started through the low-temperature starting device II at the temperature of-40 to-10 ℃.
Further, the low-temperature starting device I performs spiral winding on the pile surface of the hydrogen fuel cell through the balance air circuit to serve as a spiral heating air circuit, so that the hydrogen fuel cell is smoothly started at low temperature;
The low-temperature starting device II is connected to the outside of the reaction tank through the detachable heat exchange device, and liquid-gas or solid-liquid phase materials are used for circulation in the detachable heat exchange device, so that the hydrogen fuel cell can be smoothly started at low temperature by utilizing the heat of hydrolysis reaction.
Compared with the prior art, the invention has the following beneficial effects:
The invention discloses a hydrogen energy power supply device for normal low-temperature self-starting of hydrogen supply by hydrolysis of a hydrogen storage material, which comprises a hydrolysis hydrogen production unit, a barometric measurement control unit and a fuel cell starting output unit; the hydrogen outlet of the hydrolysis hydrogen production unit is communicated with the gas path hydrogen inlet of the gas pressure measurement control unit, the gas inlet of the fuel cell starting output unit is communicated with the gas path output of the gas pressure measurement control unit, the advantages of hydrogen production and hydrogen utilization integration can be fully exerted, and the normal operation of the system is ensured; the power interface of the hydrogen fuel cell is connected with the load part interface, and the hydrogen fuel cell directly converts chemical energy into electric energy, so that the whole device does not need external power supply, internal lithium battery power supply and other external energy consumption, and the structure is simplified; the fuel cell starting output unit is provided with a low-temperature starting device, so that the hydrogen fuel cell is started in a low-temperature environment, and the problems that the current hydrogen fuel cell power supply device is poor in environmental adaptability and cannot independently operate at low temperature can be solved. The hydrogen energy power supply device of the invention fills this gap.
Furthermore, a reaction liquid control valve is arranged on a liquid inlet pipeline in the hydrolysis hydrogen production unit and is used for controlling the reaction progress and reaction speed; the pressure is controlled by the pressure reducing valve in the control device, the pressure of the hydrogen at the air inlet is kept between 0.045 and 0.065MPa when the hydrogen fuel cell works by the pressure maintaining valve, so that the hydrogen fuel cell can work stably by ensuring enough hydrogen flow, and further the stopping and starting of the hydrogen fuel cell can be controlled, and the reaction process is controlled.
Furthermore, the graphene interface nano valve solid hydrogen storage material is preferentially used for the hydrogen source part, meanwhile, the material can be used for explaining hydrogen by normal pressure water within the temperature range of-40-85 ℃, a catalyst is not needed, and a small amount of water vapor is carried by the hydrogen released by hydrolysis to facilitate the wet reaction of the galvanic pile membrane, so that a cooling and drying device is not needed as a whole, the whole hydrogen fuel cell is small in volume and weight, and the whole device is reduced in volume.
Furthermore, the phase change material in the detachable heat exchange device uses liquid-gas phase change material or solid-liquid phase change material to conduct heat transfer circulation, and phase change materials with different boiling points can be selected according to different environment temperatures to be added through a material changing port, the material changing port is provided with a switch valve, so that the danger caused by leakage of the phase change material can be prevented, and meanwhile, the material changing port can be used for vacuumizing, the danger of combustion and explosion caused by mixing of part of the phase change material and air can be prevented; the heat preservation sheath is made of light plastic or PVC material, so that the heat transfer process of the heat exchange device can be prevented from being influenced by the ambient temperature.
The invention also discloses a power supply method of the hydrogen energy power supply device which is self-started at a low temperature and is used for supplying hydrogen by hydrolysis of the hydrogen storage material, the method can be suitable for stable operation in different environmental scenes, a great amount of heat is released when the hydrogen storage material is subjected to hydrolysis reaction, hydrogen with certain heat is released, the device firstly reacts with the heat of the hydrogen at a low temperature, a spiral heating gas circuit is arranged at a low temperature of between-10 and 0 ℃ to enable a hydrogen fuel cell to be started smoothly, and a detachable heat exchange device is added at a low temperature of between-40 and-10 ℃ to transfer a great amount of heat generated by the hydrolysis reaction in a reaction tank to the vicinity of a galvanic pile of the hydrogen fuel cell by using the phase change material so that the hydrogen fuel cell can be started smoothly at the low temperature.
Drawings
FIG. 1 is a schematic view of the internal structure of the present invention;
FIG. 2 is a schematic diagram of the balanced gas circuit heating of the present invention;
Fig. 3 is a schematic structural view of a detachable heat exchange device according to the present invention.
Wherein: the device comprises a 1-liquid inlet control valve, a 2-four-way valve, a 3-vacuumizing control valve, a 4-liquid storage tank, a 5-liquid inlet pipeline, a 6-reaction liquid control valve, a 7-reaction tank, an 8-feed inlet, a 9-unloading valve, a 10-balance gas circuit, a 1001-spiral heating gas circuit, a 11-hydrogen supply circuit, a 12-positive pressure gauge, a 13-first control valve, a 14-pressure reducing valve, a 15-second control valve, a 16-positive and negative pressure gauge, a 17-one-way valve, a 18-hydrogen fuel cell, a 19-load part, a 20-cooling fan, a 21-hydrogen storage material, a 22-detachable heat exchange device, a 701-reaction tank round bottom, a 101-phase change material, a 102-heat preservation sheath, a 103-heat conduction layer, a 104-heat transfer connecting pipeline, a 105-heat dissipation area and a 106-material exchange port.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in which it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and the claims of the present invention and the above figures are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments of the invention described herein may be implemented in sequences other than those illustrated or otherwise described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the attached drawing figures:
referring to fig. 1 to 3, a hydrogen energy power supply device for normal low temperature self-starting of hydrogen storage material hydrolysis hydrogen supply comprises a hydrolysis hydrogen production unit, a barometric pressure measurement control unit and a fuel cell starting output unit; the hydrogen outlet of the hydrolysis hydrogen production unit is communicated with the gas path hydrogen inlet of the air pressure measurement control unit; an air inlet of the fuel cell starting output unit is communicated with an air channel output port of the air pressure measurement control unit;
The hydrolysis hydrogen production unit comprises a liquid inlet control valve 1, a four-way valve 2, a vacuumizing control valve 3, a liquid storage tank 4, a liquid inlet pipeline 5, a reaction liquid control valve 6, a reaction tank 7, a reaction tank round bottom 701, a feed inlet 8 and a balance gas circuit 10, wherein a hydrogen storage material 21 is arranged in the reaction tank 7; the four-way valve 2 is arranged above the liquid storage tank 4, one way of the four-way valve 2 is connected with the liquid inlet control valve 1, the other way of the four-way valve is connected with the vacuumizing control valve 3 to control the vacuumizing port, the other way of the four-way valve is connected with the balance gas circuit 10, the reaction tank 7 and the liquid storage tank 4 are directly connected through the balance gas circuit 10 to realize air pressure balance, the lower part of the liquid storage tank 4 is connected with the reaction tank 7 through the liquid inlet pipeline 5, the reaction liquid control valve 6 is arranged on the liquid inlet pipeline 5 to control liquid to enter the reaction tank 7, the gas circuit outlet of the hydrogen supply pipeline 11 and the charging port 8 are arranged on the reaction tank 7, the unloading valve 9 is arranged at the gas circuit outlet of the hydrogen supply pipeline 11, the bottom of the reaction tank 7 is an arc round bottom, and the contact area of the reaction liquid and the hydrogen storage material 21 is increased to be favorable for accelerating the hydrogen production speed of the hydrolysis reaction.
The air pressure measurement control unit comprises an unloading valve 9, a hydrogen supply path 11, a positive pressure gauge 12, a first control valve 13, a pressure reducing valve 14, a second control valve 15, a positive and negative pressure gauge 16 and a one-way valve 17. The positive pressure gauge 12 and the positive pressure gauge 16 are arranged on the hydrogen supply path 11, the middle is divided into two parallel branches, one branch is a pressure reducing valve 14 and a first control valve 13, the other branch is a second control valve 15, and a one-way valve 17 is arranged in front of a hydrogen inlet of the hydrogen fuel cell 18.
The fuel cell start-up output unit includes a hydrogen fuel cell 18, a load portion 19, and a low-temperature start-up unit, and a power supply interface of the hydrogen fuel cell 18 is connected to the load portion 19 interface through a converter or the like. The low-temperature starting unit comprises a low-temperature starting device I and a low-temperature starting device II, wherein the low-temperature starting device I comprises a cooling fan 20 and a spiral heating gas circuit 1001, the low-temperature starting device II comprises a detachable heat exchange device 22, and the detachable heat exchange device 22 comprises a phase change material 101, a heat preservation sheath 102, a heat conduction layer 103, a heat transfer connecting pipeline 104, a heat dissipation area 105 and a material exchange port 106; the heat conduction layer 103, the phase change material 101, the heat conduction layer 103 and the heat preservation sheath 102 are sequentially arranged outside the reaction tank 7 from inside to outside, and the material changing port 106 is arranged at one side of the heat preservation sheath 102; the heat dissipation area 105 is arranged in a gap area between the pile face of the hydrogen fuel cell 18 and the spiral heating gas circuit 1001; the heat transfer connecting pipeline 104 is formed by respectively connecting a circular pipeline with the heat conducting layers 103 on two sides of the diameter of the top of the reaction tank 7 in an opening way, and the circular pipeline is intersected with the heat radiating area 105 through the balance gas circuit 10, and the rest heat conducting layers 103 on the top of the reaction tank are all sealed; the internal phase change material 101 uses liquid-gas phase change material or solid-liquid phase change material to conduct heat transfer circulation, phase change materials with different boiling points are selected according to different environmental temperatures and are added through a material changing port 106, the material changing port 106 is provided with a switch valve to prevent the internal phase change material from leaking to cause danger, and meanwhile, the material changing port can be used for vacuumizing to prevent the danger of combustion explosion and the like caused by mixing of part of phase change materials and air; the heat conducting layer 103 is coated on the outside of the internal phase change material by using a heat conducting silica gel sheet or an alumina ceramic sheet with high heat conductivity, meanwhile, a heat insulating sheath 102 is added on the outside of the heat conducting layer 103 and the outside of the heat transfer pipeline 104, and the heat insulating sheath 102 is made of light plastic or PVC material to prevent the heat transfer process of the heat exchange device from being influenced by the ambient temperature.
The shell of the reaction tank 7 is made of materials with good alkali resistance and heat conduction performance, such as stainless steel; the four-way valve 2 is normally open and is connected with four pipelines; the liquid inlet control valve 1 and the vacuumizing control valve 3 are ball valves for controlling the corresponding pipelines to be opened and closed; the positive pressure gauge 12 is used for displaying the pressure in the system before the pressure reducing valve, a mechanical instrument is adopted, the positive pressure gauge 16 is used for displaying the air tightness of the pressure maintaining detection system and determining the output pressure after the pressure reducing valve when the system is vacuumized, and the mechanical instrument is also used for avoiding the external power supply or the internal lithium battery power supply and preventing the abnormal work at low temperature; the unloading valve 9 can automatically release pressure after reaching the set pressure value so as to keep the system safe; the pressure reducing valve 14 is a light pressure reducing valve, and is used for reducing and stabilizing the output pressure, and is adapted to the normal working pressure range of the hydrogen fuel cell 18, so that the hydrogen fuel cell can work normally; the one-way valve 17 is used for preventing the air flow from flowing backwards; the first control valve 13 is a ball valve, and is used for controlling the hydrogen supply of the hydrogen fuel cell 18 to stop and start, and the first control valve 13 can be opened to supply the hydrogen to the hydrogen fuel cell 18 to work after the opening pressure of the one-way valve is reached; the second control valve 15 is also a ball valve, and is used for being opened when vacuumizing, so that the vacuumizing condition can be conveniently observed through the positive and negative pressure gauge 16, and closed when normal working, high-pressure hydrogen is prevented from directly entering the hydrogen fuel cell 18; the hydrogen fuel cell 18 is a proton exchange membrane fuel cell, the specific power can be matched according to the requirement, and the normal working pressure range of the hydrogen at the air inlet is 0.045-0.065 MPa; the voltage and power of the load portion 19 should be matched to the hydrogen fuel cell 18; the inside of the liquid storage tank 4 is reaction liquid, and is used as a source part for controlling the reaction to stop and start, a balance gas circuit 10 is arranged between the liquid storage tank 4 and the reaction tank 7, so that the liquid can be ensured not to be influenced by the pressure difference between the inside of the reaction tank body and the inside of the liquid storage tank body, and the non-liquid part of the liquid storage tank 4 is used as a gas storage tank; the reaction liquid control valve 6 is a metering valve or a needle valve, controls the reaction liquid to enter the reaction tank 7, and can measure the volume of the liquid according to the requirement for controlling the reaction progress and reaction speed.
The hydrogen storage material 21 is a graphene interface nano valve solid hydrogen storage material, the material takes high-activity light metal hydride as a raw material, and a graphene interface nano valve structure is established at different groups of interfaces so as to realize the hydrogen release controllability of the hydrogen storage material, and a catalyst is not needed in the hydrolysis reaction. Other suitable hydrolyzed solid state hydrogen storage materials may also be used.
The invention also discloses a power supply method of the hydrogen energy power supply device which is started at a low temperature and is used for supplying hydrogen by hydrolysis of the hydrogen storage material, wherein the power supply method comprises a normal temperature power supply mode above 0 ℃ and a subzero low temperature power supply mode:
The direct starting device can be operated in a normal temperature power supply mode above 0 ℃, the heat of the balance gas circuit 10 does not influence the normal temperature operation of the hydrogen fuel cell 18, the starting in a subzero low temperature power supply mode is divided into two cases, when one is at the temperature of minus 10-0 ℃, the valve is controlled and the spiral winding direction is carried out on the pile surface of the back surface of the cooling fan 20 of the hydrogen fuel cell 18 through the balance gas circuit 10 to be used as a spiral heating gas circuit 1001, as shown in fig. 2; when the temperature is lower than-40 ℃ to-10 ℃, a detachable heat exchange device 22 is added to the outside of the reaction tank 7, as shown in fig. 3, a liquid-gas or solid-liquid phase material 101 is used for circulation, and a heat dissipation area 105 is arranged in a gap area between the pile face of the hydrogen fuel cell 18 and the spiral heating gas circuit 1001, so that the hydrogen fuel cell 18 is smoothly started at low temperature by utilizing hydrolysis reaction heat.
According to the above technical scheme, as shown in fig. 1 to 3, the embodiment provides a hydrogen energy power supply device and a power supply method for self-starting at a low temperature for hydrogen supply by hydrolysis of a hydrogen storage material, which utilize the heat of hydrolysis reaction of a hydrogen source to realize smooth starting of a hydrogen fuel cell 18 at a low temperature and continuous and stable operation of a load part 19.
Example 1:
At the normal temperature above 0 ℃, all valves are guaranteed to be in a closed state before reaction, a liquid inlet control valve 1 is opened, liquid required by the reaction is injected into a liquid storage tank 4, pure water (under the condition of using a graphene interface nano valve solid hydrogen storage material) can be used at normal temperature, and the liquid can be added at one time or can be added in the middle; adding hydrogen storage material 21 from a charging port 8 of the reaction tank to the reaction tank 7; the vacuumizing control valve 3 and the second control valve 15 are opened, the air tightness of the vacuumizing inspection device is carried out from a branch for carrying out the vacuumizing control valve 3, the integral air tightness of the device is confirmed through the positive and negative pressure gauge 16, on the premise of good air tightness of the system, the vacuumizing control valve 3 and the second control valve 15 are confirmed to be closed, the reaction liquid control valve 6 on the liquid inlet pipeline 5 is adjusted, the reaction liquid is added into the reaction tank 7, the hydrogen storage material 21 and the reaction liquid carry out reaction water to explain hydrogen, the first control valve 13 is opened when the positive pressure gauge is stable in the indication, the positive and negative pressure gauge 16 is also observed, the first control valve 13 is closed in time for pressure maintaining when the positive pressure gauge is unstable, the positive and negative pressure gauge 16 is stable in the indication, and the output end of the hydrogen fuel cell 18 is connected with the load part 19 with matched power, so that the load part 19 can work normally.
In an environment below 0 ℃ of the hydrogen fuel cell 18, water is generated at the cathode of the cell and is transported outwards, at this time, water in the cell can freeze and cannot be removed from the cell, and accumulation in the cell can cause a catalytic layer to form ice to cover the active surface of the catalytic layer, so that reactant gas is reduced or prevented from reaching a reaction interface, and the hydrogen fuel cell 18 cannot be started; on the other hand, the humidifying water can block the flow channel to prevent the transmission of the reaction gas; most importantly, ice crystals formed in the water inside the stack can damage the stack, thereby rendering the hydrogen fuel cell 18 inoperable.
Example 2:
At the temperature of-10 to 0 ℃, a detachable antifreezing jacket can be added between the gas path outlet of the reaction tank 7and the spiral heating gas path 1001 to reduce heat loss on the middle gas path, which is more beneficial to cold starting of the hydrogen fuel cell 18, meanwhile, the spiral winding of part of the balance gas path 10 to the spiral heating gas path 1001 also increases the volume of the balance gas path equivalent to increasing the gas buffer volume of the whole device, so that the safety of the whole device is higher, all valves are ensured to be in a closed state before reaction, the liquid inlet control valve 1 is opened, liquid needed by the reaction is injected into the liquid storage tank 4, the reaction liquid with different dosages of antifreezing agent is added below 0 ℃ to prevent the liquid from freezing and failing to flow into the reaction tank 7, and the reaction tank can be added at one time or be supplemented in the middle; adding hydrogen storage material 21 from a charging port 8 of the reaction tank to the reaction tank 7; the vacuumizing control valve 3 and the second control valve 15 are opened, the airtightness of the vacuumizing inspection device is carried out from a branch for carrying out the vacuumizing control valve 3, the whole airtightness of the device is confirmed through the positive and negative pressure gauges 16, on the premise that the airtightness of the system is good, the vacuumizing control valve 3 and the second control valve 15 are confirmed to be closed, the reaction liquid control valve 6 on the liquid inlet pipeline 5 is adjusted, the reaction liquid is added into the reaction tank 7, the hydrogen storage material 21 and the reaction liquid carry out reaction water to interpret hydrogen, the reaction is used for adding heat for a period of time, the first control valve 13 is opened according to the readings of the positive pressure gauge 12 and the positive and negative pressure gauge 16 when the readings of the positive pressure gauge 12 are stable and the ambient temperature near the electric pile surface of the hydrogen fuel cell 18 is close to 0 ℃, the first control valve 13 is closed in time when the readings of the positive and negative pressure gauge 16 are observed, the output end of the hydrogen fuel cell 18 is connected to the load part 19 with power matching under the condition that the readings of the positive and negative pressure gauge 16 are stable, and the load part 19 can work normally.
Example 3:
When the temperature is between minus 40 ℃ and minus 10 ℃, the detachable heat exchange device 22 is correctly placed before the reaction, phase change materials 101 with different boiling points are selected according to different environmental temperatures in the detachable heat exchange device and are added into the heat exchange device through the material changing port 106, all valves of the whole device are guaranteed to be in a closed state, the liquid inlet control valve 1 is opened, liquid required by the reaction is injected into the liquid storage tank 4, the liquid is prevented from being frozen by using the reaction liquid added with different doses of antifreezing agent below minus 10 ℃ and cannot flow into the reaction tank 7, and the detachable heat exchange device can be added at one time or can be added in the middle; adding hydrogen storage material 21 from a charging port 8 of the reaction tank to the reaction tank 7; the vacuumizing control valve 3 and the second control valve 15 are opened, the airtightness of the vacuumizing inspection device is carried out from a branch for carrying out the vacuumizing control valve 3, the whole airtightness of the device is confirmed through the positive and negative pressure gauge 16, on the premise that the airtightness of the system is good, the vacuumizing control valve 3 and the second control valve 15 are confirmed to be closed, the reaction liquid control valve 6 on the liquid inlet pipeline 5 is adjusted, the reaction liquid is added into the reaction tank 7, the hydrogen storage material 21 and the reaction liquid carry out reaction water to explain hydrogen, the reaction heat is fully released after waiting for a period of time for reaction, the heat exchange requirement can be met, the first control valve 13 is opened when the indication of the positive pressure gauge 12 and the positive and negative pressure gauge 16 is stable and the ambient temperature near the electric pile surface of the hydrogen fuel cell 18 is close to 0 ℃, meanwhile, the first control valve 13 is closed in time for pressure maintaining when the indication of the positive and negative pressure gauge 16 is observed, under the condition that the indication of the positive pressure gauge 16 is stable, and the output end of the hydrogen fuel cell 18 is connected with the load part 19 with power matching, so that the load part 19 can work normally.
The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (7)
1. The hydrogen energy power supply device for the normal low-temperature self-starting of the hydrogen storage material for hydrogen supply by hydrolysis is characterized by comprising a hydrolysis hydrogen production unit, a barometric measurement control unit and a fuel cell starting output unit; the hydrogen outlet of the hydrolysis hydrogen production unit is communicated with the gas path hydrogen inlet of the air pressure measurement control unit; an air inlet of the fuel cell starting output unit is communicated with an air channel output port of the air pressure measurement control unit;
the hydrolysis hydrogen production unit comprises a liquid storage tank (4) and a reaction tank (7), and the reaction tank (7) is connected with the liquid storage tank (4) through a balance gas circuit (10);
The fuel cell starting output unit comprises a hydrogen fuel cell (18), a load part (19) and a low-temperature starting unit, wherein the low-temperature starting unit is used for starting the hydrogen fuel cell (18) at a low temperature, and a power interface of the hydrogen fuel cell (18) is connected with an interface of the load part (19);
The low-temperature starting unit comprises a low-temperature starting device I and a low-temperature starting device II, wherein the hydrogen fuel cell (18) is started through the low-temperature starting device I at the temperature of-10 to 0 ℃, and the hydrogen fuel cell (18) is started through the low-temperature starting device II at the temperature of-40 to-10 ℃; the low-temperature starting device I comprises a cooling fan (20) and a spiral heating air circuit (1001), wherein the spiral heating air circuit (1001) is arranged on the pile surface of the hydrogen fuel cell (18), and the cooling fan (20) is arranged on the reverse side of the pile surface of the hydrogen fuel cell (18); the low-temperature starting device II is a detachable heat exchange device (22) arranged outside the reaction tank (7), and the detachable heat exchange device (22) consists of a phase change material (101), a heat preservation jacket (102), a heat conduction layer (103), a heat transfer connecting pipeline (104), a heat dissipation area (105) and a material exchange port (106); the low-temperature starting device I is spirally wound on the pile surface of the hydrogen fuel cell (18) through the balance gas circuit (10) to serve as a spiral heating gas circuit (1001), so that the hydrogen fuel cell (18) is smoothly started at low temperature; the low-temperature starting device II is added to the outside of the reaction tank (7) through a detachable heat exchange device (22), and the inside of the detachable heat exchange device (22) is circulated by using a liquid-gas or solid-liquid phase material (101), so that the hydrogen fuel cell (18) is smoothly started at low temperature by utilizing the heat of hydrolysis reaction;
the heat conduction layer (103), the phase change material (101), the heat conduction layer (103) and the heat preservation sheath (102) are sequentially arranged outside the reaction tank (7) from inside to outside, the material changing port (106) is arranged at one side of the heat preservation sheath (102), and the heat dissipation area (105) is arranged in a gap area between a pile surface of the hydrogen fuel cell (18) and the spiral heating gas circuit (1001); the heat transfer connecting pipeline (104) is intersected with the heat dissipation area (105).
2. The normal low temperature self-starting hydrogen energy power supply device for hydrogen storage material hydrolysis hydrogen supply according to claim 1 is characterized in that a four-way valve (2) is connected above a liquid storage tank (4) through a pipeline, one way of the four-way valve (2) is connected with a liquid inlet control valve (1), the other way is connected with a vacuumizing control valve (3), the other way is connected with a balance gas circuit (10), the lower part of the liquid storage tank (4) is connected with a reaction tank (7) through a liquid inlet pipeline (5), and a reaction liquid control valve (6) capable of controlling the liquid flow rate is arranged on the liquid inlet pipeline (5);
The reaction tank (7) is provided with a gas path outlet of a hydrogen supply path (11) and a charging port (8), and the gas path outlet of the hydrogen supply path (11) is provided with an unloading valve (9); a hydrogen storage material (21) is arranged in the reaction tank (7);
The hydrogen storage material (21) is one of a graphene interface nano valve solid hydrogen storage material, sodium borohydride or magnesium hydride.
3. The hydrogen energy power supply device capable of being started at a low temperature and self-starting for hydrogen supply by hydrolysis of a hydrogen storage material according to claim 1, wherein the phase change material (101) is a liquid-gas phase change material or a solid-liquid phase change material, the phase change material is added through a material changing port (106), and the material changing port (106) is provided with a switch valve.
4. The hydrogen energy power supply device capable of self-starting at a normal low temperature for hydrogen supply by hydrolysis of a hydrogen storage material according to claim 1, wherein the heat conducting layer (103) is coated outside the phase change material (101), and the heat conducting layer (103) is made of a heat conducting silica gel sheet or an alumina ceramic sheet;
in the detachable heat exchange device (22), a heat insulation sheath (102) is added outside the heat conduction layer (103) and outside the heat transfer connecting pipeline (104), and the heat insulation sheath (102) is made of light plastic or PVC material.
5. The hydrogen energy power supply device for normal low temperature self-starting of hydrogen storage material hydrolysis hydrogen supply according to claim 1, wherein the air pressure measurement control unit comprises a plurality of control devices which are all arranged on a pipeline between the reaction tank (7) and the fuel cell starting output unit;
The control device comprises an unloading valve (9), a positive pressure gauge (12), a first control valve (13), a pressure reducing valve (14), a second control valve (15), a positive pressure gauge (16) and a one-way valve (17), wherein the positive pressure gauge (12) and the positive pressure gauge (16) are arranged on a hydrogen supply path (11), the middle of the positive pressure gauge (12) and the middle of the positive pressure gauge (16) are divided into two parallel branches, one branch is the pressure reducing valve (14) and the first control valve (13), the other branch is the second control valve (15), and the one-way valve (17) is arranged in front of a hydrogen inlet of a hydrogen fuel cell (18).
6. The hydrogen energy power supply device for normal low temperature self-starting of hydrogen storage material hydrolysis hydrogen supply according to claim 1, wherein the hydrogen fuel cell (18) is a proton exchange membrane fuel cell, and the normal working pressure range of hydrogen at the air inlet of the hydrogen fuel cell (18) is 0.045-0.065 MPa; the load section (19) should be matched to the hydrogen fuel cell (18) power.
7. The power supply method of the normally low temperature self-starting hydrogen energy power supply device for hydrogen supply by hydrolysis of a hydrogen storage material according to any one of claims 1 to 6, wherein the power supply method of the normally low temperature self-starting hydrogen energy power supply device for hydrogen supply by hydrolysis of the hydrogen storage material comprises a normal temperature power supply mode and a subzero low temperature power supply mode above 0 ℃; directly starting a hydrogen fuel cell (18) in a normal temperature power supply mode at a temperature above 0 ℃;
starting in the subzero low-temperature power supply mode is divided into two cases, wherein one case is that the hydrogen fuel cell (18) is started through the low-temperature starting device I at the temperature of-10 to 0 ℃, and the other case is that the hydrogen fuel cell (18) is started through the low-temperature starting device II at the temperature of-40 to-10 ℃.
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