CN113594504B - Method for storing and quickly starting fuel cell stack under low-temperature condition - Google Patents
Method for storing and quickly starting fuel cell stack under low-temperature condition Download PDFInfo
- Publication number
- CN113594504B CN113594504B CN202111139906.8A CN202111139906A CN113594504B CN 113594504 B CN113594504 B CN 113594504B CN 202111139906 A CN202111139906 A CN 202111139906A CN 113594504 B CN113594504 B CN 113594504B
- Authority
- CN
- China
- Prior art keywords
- temperature
- phase change
- galvanic pile
- change material
- phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
- H01M8/04052—Storage of heat in the fuel cell system
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
- B60L50/00—Electric propulsion with power supplied within the vehicle
- B60L50/50—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells
- B60L50/70—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells using power supplied by fuel cells
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
- B60L58/00—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles
- B60L58/30—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles for monitoring or controlling fuel cells
- B60L58/31—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles for monitoring or controlling fuel cells for starting of fuel cells
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
- B60L58/00—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles
- B60L58/30—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles for monitoring or controlling fuel cells
- B60L58/32—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles for monitoring or controlling fuel cells for controlling the temperature of fuel cells, e.g. by controlling the electric load
- B60L58/34—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles for monitoring or controlling fuel cells for controlling the temperature of fuel cells, e.g. by controlling the electric load by heating
-
- 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
- H01M8/04253—Means for solving freezing problems
-
- 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
- H01M8/043—Processes for controlling fuel cells or fuel cell systems applied during specific periods
- H01M8/04302—Processes for controlling fuel cells or fuel cell systems applied during specific periods applied during start-up
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02T90/40—Application of hydrogen technology to transportation, e.g. using fuel cells
Landscapes
- Engineering & Computer Science (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Transportation (AREA)
- Mechanical Engineering (AREA)
- Fuel Cell (AREA)
Abstract
The invention provides a method for storing and quickly starting a fuel cell stack under a low-temperature condition. Loading an inert gas bottle on the vehicle, providing inert gas to sweep the galvanic pile after the galvanic pile is switched to a shutdown state, wherein the inert gas stays in the galvanic pile, and when the environmental temperature is lower, the temperature around the galvanic pile is reduced in the shutdown process, the phase change material is subjected to phase change, and latent heat is released to preserve heat of the galvanic pile; when the galvanic pile needs to be started under the low-temperature condition, the galvanic pile is directly heated by triggering the phase change material to generate phase change, so that the galvanic pile can be quickly started under the low-temperature condition of-30-0 ℃ and enters a normal working state. The method can prevent the interior of the galvanic pile from icing for a long time, and prolong the service life of the membrane electrode; meanwhile, the low-temperature starting time is shortened, and the energy consumption is reduced, so that the adaptability of the fuel cell stack under the low-temperature condition is improved.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a method for storing and quickly starting a fuel cell stack under a low-temperature condition.
Background
After a Proton Exchange Membrane Fuel Cell (PEMFC) undergoes a chemical reaction, water is generated and mainly distributed in a membrane electrode, a diffusion layer and a flow channel of the fuel cell, and is easily frozen below zero degrees. The frozen membrane electrode surface can wrap catalyst particles to reduce the activity of the catalyst, and meanwhile, the frozen membrane electrode can cause volume expansion, and after the ice is melted into water, the volume can be reduced, and the membrane electrode can be irreversibly damaged due to repeated phase change. And the icing in the diffusion layer and the flow channel can block a gas-liquid mass transfer channel, so that reaction gas cannot reach a reaction site, the fuel cell cannot normally operate, and the low-temperature start fails.
At present, the removal of redundant liquid water in the battery through shutdown purging becomes a necessary link for low-temperature cold start of the fuel battery. In the prior art, dry air purging is generally adopted, and moisture needs to exist in a membrane electrode for a long time and needs to be in a proper amount. If the moisture in the membrane electrode is blown too much, the membrane drying phenomenon can be caused, the instantaneous performance is influenced if the moisture is too much, and the local hot spot of the proton exchange membrane is caused if the moisture is too much, so that the permanent damage is generated. Therefore, the accurate judgment of the dry and wet degree of the membrane electrode and the strict control of the purging time increase the operation difficulty. Meanwhile, hydrogen and air exist on two sides of the membrane electrode at the same time easily due to air purging, a hydrogen-air interface is formed at the anode end, a great damage effect is achieved on the battery, and the catalytic layer and the carbon carrier of the galvanic pile can be corroded due to the generated open-circuit voltage. Although the patent with application No. 201910735902.2 entitled auxiliary system for fuel cell and method for rapidly purging shutdown cathode, it also mentions that the dry-wet condition of the cathode of the stack is indirectly fed back by using a stack air humidity sensor, and the air temperature is raised without passing through an intercooler and a humidifier to reduce the humidity, thereby speeding up the purging of the cathode moisture of the stack, but the adverse effect of air infiltration into the anode side is still not solved.
In addition, various low-temperature storage and starting technologies of the fuel cell stack are available at present, and mainly focus on direct preheating by external heating methods such as an electric heating wire and the like during starting, which are only heat preservation through a heat insulating material, and have the defects of poor heat preservation effect or high extra energy consumption and the like. Although the invention patent with application number 201610749589.4, entitled proton exchange membrane fuel cell with low-temperature start function, mentions that microcapsule phase change heat storage material is coated on the fuel cell main body and the cathode and anode bipolar plates, the general phase change material has the limitation of phase change cycle times, the operation is not beneficial to the replacement of the phase change material in the later period, the coating operation process is complicated, in addition, because the electric pile is positioned in the fuel cell system, the direct contact with illumination is difficult, and the photo-thermal conversion heat preservation fiber on the surface layer has difficult effect in the practical application process.
Disclosure of Invention
In order to solve the problems, the invention adopts the following technical scheme: a method for storing and quickly starting a fuel cell stack under low temperature conditions comprises the following specific steps: s1, adding a phase change material into a packaging shell of the galvanic pile, and arranging the galvanic pile with the packaging shell on a vehicle;
s2, loading an inert gas bottle on the vehicle, and after the galvanic pile is switched from the working state to the shutdown state, providing inert gas through the inert gas bottle to purge the galvanic pile, wherein after purging is finished, the inert gas stays in the galvanic pile;
s3, when the environment temperature is low, the phase change material changes phase with the reduction of the temperature around the galvanic pile in the shutdown process, latent heat is released to preserve heat of the galvanic pile, when the galvanic pile needs to be started under the low temperature condition, the phase change material is triggered to change phase to directly heat the galvanic pile, so that the galvanic pile can be quickly started under the low temperature condition to enter a normal working state, and the low temperature condition is-30-0 ℃.
Further, in the step S1, the package housing includes an upper plate, a lower plate, a left sealing plate and a right sealing plate, both ends of the electric pile are provided with end plates, one side of the upper plate is connected with one side of the lower plate through the left sealing plate, the other side of the upper plate is connected with the other side of the lower plate through the right sealing plate, the upper plate, the lower plate, the left sealing plate, the right sealing plate and the two end plates form a closed space, the galvanic pile is positioned in the closed space, the upper plate and the lower plate are both double-layer plates, the phase change material comprises a first phase change material and a second phase change material, the first phase change material is arranged in the lower plate, the second phase change material is arranged in the upper plate, and both the inner layer of the upper plate and the inner layer of the lower plate are heat insulation layers.
Furthermore, the heat-insulating layer is made of rigid polyurethane foam.
Further, the first phase change material is a decanol-palmitic acid/expanded graphite ternary composite organic phase change material, and the second phase change material is a palmitic acid/expanded graphite composite organic phase change energy storage material.
Further, in the step S2, a purge system is installed on the vehicle, and the purge system is used for controlling the inert gas bottle to purge the stack.
Further, the purging system includes a pressure reducing valve, a first solenoid valve, a second solenoid valve, a first control valve, a second control valve, a first three-way valve, a second three-way valve, a third three-way valve, a back pressure valve, a first flow sensor, a second flow sensor, a first pressure sensor, a second pressure sensor, a first humidity sensor, a second humidity sensor, a first temperature sensor, a second temperature sensor, and a third temperature sensor, the inert gas bottle, the first solenoid valve, the pressure reducing valve, and the first three-way valve are sequentially connected, the first three-way valve connects the first control valve and the second control valve, the first control valve connects the second three-way valve, the second three-way valve connects with an external air inlet pipeline, and the second three-way valve connects with the first flow sensor, the first flow sensor connects with the first pressure sensor, the first pressure sensor is connected with the first temperature sensor, and the first temperature sensor is connected with the galvanic pile; the second control valve is connected the third three-way valve, the third three-way valve is connected with outside hydrogen inlet pipeline, just the third three-way valve is connected the second flow sensor, the second flow sensor is connected the second pressure sensor, the second pressure sensor with the pile is connected, the second temperature sensor with the pile is connected, just the second temperature sensor with first humidity transducer is connected, first humidity transducer with the back pressure valve is connected, the third temperature sensor with the pile is connected, just the third temperature sensor with the second humidity sensor is connected, the second humidity sensor with the second solenoid valve is connected.
Further, the inert gas is nitrogen.
Further, in the step S2, when the temperatures measured by the second temperature sensor and the third temperature sensor are lower than 40 ℃, and when the humidity measured by the first humidity sensor and the second humidity sensor is lower than 20%, the first solenoid valve, the second solenoid valve, and the back pressure valve are closed.
Further, in the step S3, the phase change material is heated to the phase change temperature through temperature compensation by turning on the phase change trigger, and then the controllable release of the latent heat of phase change is performed, so as to heat the stack.
Further, the phase change trigger is a thermistor.
The invention has the beneficial effects that: the method can prevent the interior of the galvanic pile from icing for a long time, and prolong the service life of the membrane electrode; meanwhile, the low-temperature starting time is shortened, and the energy consumption is reduced, so that the adaptability of the fuel cell stack under the low-temperature condition is improved.
Drawings
The figures further illustrate the invention, but the examples in the figures do not constitute any limitation of the invention.
FIG. 1 is a flow chart of the present invention.
FIG. 2 is a schematic diagram of the connections of a purge system according to an embodiment.
Fig. 3 is an exploded view of an exemplary stack and a package housing.
Detailed Description
The technical solutions of the present invention will be further described below with reference to the accompanying drawings of the embodiments of the present invention, and the present invention is not limited to the following specific embodiments. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
As shown in fig. 1, a method for storing and rapidly starting a fuel cell stack 1 under low temperature conditions includes the following steps:
s1, adding a phase change material into a packaging shell of the galvanic pile, and arranging the galvanic pile with the packaging shell on a vehicle;
that is to say, the organic phase change material combined with the expanded graphite is added in the packaging shell, so that the phase change material is well wrapped in the expanded graphite, the leakage phenomenon cannot occur in the heat treatment process, the adsorption effect is good, the stable solid shape can be kept before and after phase change, and the packaging shell has no flowability. When the electric pile 1 works normally, the phase-change material absorbs heat and changes phase.
And S2, loading an inert gas bottle 4 on the vehicle, and after the electric pile 1 is switched from the working state to the shutdown state, providing inert gas through the inert gas bottle 4 to purge the electric pile 1, wherein after the purging is finished, the inert gas stays in the electric pile 1.
That is to say, when the electric pile 1 is shut down, the electric pile 1 is purged immediately without cooling, and the residual moisture in most of the electric pile 1 is removed in a short time by means of the residual heat of the electric pile 1. In addition, after the purging is stopped, the low-pressure inert gas stays in the galvanic pile 1 for a long time, and the secondary purging is avoided after the startup.
S3, when the environment temperature is low, the phase change material changes phase with the reduction of the temperature around the galvanic pile in the shutdown process, latent heat is released to preserve the temperature of the galvanic pile, when the galvanic pile 1 needs to be started under the low temperature condition, the phase change material is triggered to change phase to directly heat the galvanic pile 1, so that the galvanic pile 1 can be quickly started under the low temperature condition to enter a normal working state, and the low temperature condition is-30-0 ℃.
That is to say, when the ambient temperature is lower, along with the gradual reduction of shutdown process pile 1 surrounding temperature, the phase change material takes place reverse phase transition, releases the heat and keeps warm for the pile heating, makes the pile can store under the low temperature condition for a long time and does not take place to freeze. When the low-temperature starting is carried out, the second phase change material added into the packaging shell of the electric pile 1 is subjected to phase change to release heat, so that the electric pile 1 is directly heated, the efficiency and the utilization rate of the heat are improved, the consumption of extra heat is reduced, and the low-temperature starting time is shortened.
Therefore, the method can prevent the interior of the electric pile 1 from icing for a long time, and prolong the service life of the membrane electrode; meanwhile, the low-temperature starting time is shortened, and the energy consumption is reduced, so that the adaptability of the fuel cell stack 1 under the low-temperature condition is improved.
Example 1
As shown in fig. 3, a method for storing and rapidly starting a fuel cell stack 1 under low temperature conditions includes the following steps:
s1, adding a phase change material into a packaging shell of the galvanic pile, and arranging the galvanic pile with the packaging shell on a vehicle;
that is to say, the organic phase change material combined with the expanded graphite is added in the packaging shell, so that the phase change material is well wrapped in the expanded graphite, the leakage phenomenon cannot occur in the heat treatment process, the adsorption effect is good, the stable solid shape can be kept before and after phase change, and the packaging shell has no flowability. Specifically, the package housing includes an upper plate 12, a lower plate 11, a left sealing plate 13 and a right sealing plate 14, end plates are disposed at two ends of the stack 1, one side of the upper plate 12 is connected with one side of the lower plate 11 through the left sealing plate 13, the other side of the upper plate 12 is connected with the other side of the lower plate 11 through the right sealing plate 14, the upper plate 12, the lower plate 11, the left sealing plate 13, the right sealing plate 14 and the two end plates form a closed space, the stack 1 is located in the closed space, the upper plate 12 and the lower plate 11 are both double-layer plates, the phase change material includes a first phase change material and a second phase change material, the first phase change material is disposed in the lower plate 11, and the second phase change material is disposed in the upper plate 12. Further, the inner layer of the upper plate 12 and the inner layer of the lower plate 11 are both heat insulation layers. The first phase change material is a decyl alcohol-palmitic acid/expanded graphite ternary composite organic phase change material. The phase change temperature is 2.7 ℃, the phase change latent heat is 193.9J/g, and the thermal conductivity is 1.416 W. (m.K)-1. The second phase change material is palmitic acid/expanded graphite compositeAnd (4) mechanical phase change energy storage materials. The phase transition temperature is 60.8 ℃, the phase transition latent heat is 148J/g, and the thermal conductivity is 0.6W (m.K)-1. When the ambient temperature is below zero and the galvanic pile 1 is cooled to below 60 ℃, the second phase change material is converted from the liquid phase to the solid phase to emit heat; when the galvanic pile is cooled to below 2 ℃, the first phase change material is changed from a liquid phase to a solid phase to emit heat. Due to the large thermal conductivity of the composite phase change material, the heat release rate is high. And the coefficient of heat conductivity of the heat insulation and heat preservation material is lower, and the heat can be slowly transferred to the galvanic pile 1, so that the temperature of the galvanic pile 1 can rise, but the rising temperature can not be higher, so that the inside of the galvanic pile 1 can be preserved above zero for a long time without icing, and the heat preservation effect is achieved.
That is to say, through upper plate 12 and lower floor 11, can realize effect such as dustproof, insulating, thermal-insulated, shock attenuation, safe leak protection well, further, because upper plate 12 and lower floor 11 are the double-deck board, and the inlayer of upper plate 12 and the inlayer of lower floor 11 are the heat preservation, consequently can keep warm to pile 1 well.
And S2, loading an inert gas bottle 4 on the vehicle, and after the electric pile 1 is switched from the working state to the shutdown state, providing inert gas through the inert gas bottle 4 to purge the electric pile 1, wherein after the purging is finished, the inert gas stays in the electric pile 1.
That is to say, when the electric pile 1 is shut down, the electric pile 1 is purged immediately without cooling, and the residual moisture in most of the electric pile 1 is removed in a short time by means of the residual heat of the electric pile 1. In addition, after the purging is stopped, the low-pressure inert gas stays in the galvanic pile 1 for a long time, and the secondary purging is avoided after the startup.
S3, when the environment temperature is low, the phase change material changes phase with the reduction of the temperature around the galvanic pile in the shutdown process, latent heat is released to preserve the temperature of the galvanic pile, when the galvanic pile 1 needs to be started under the low temperature condition, the phase change material is triggered to change phase to directly heat the galvanic pile 1, so that the galvanic pile 1 can be quickly started under the low temperature condition to enter a normal working state, and the low temperature condition is-30-0 ℃.
That is, when the stack 1 operates normally, the phase change material absorbs heat and undergoes phase change; in the shutdown process, the ambient temperature is below 0 ℃, and when the ambient temperature of the galvanic pile 1 is reduced to 60 ℃, the phase change material carries out reverse phase change and releases heat; when the ambient temperature of the galvanic pile 1 is reduced to 2 ℃, the phase-change material carries out reverse phase change and releases heat to heat the galvanic pile, so that the galvanic pile 1 can be stored for a long time under the low-temperature condition without freezing, thereby playing a role in heat preservation. When the low-temperature starting is carried out, the second phase change material added into the packaging shell of the electric pile 1 is subjected to phase change to release heat, so that the electric pile 1 is directly heated, the efficiency and the utilization rate of the heat are improved, the consumption of extra heat is reduced, and the low-temperature starting time is shortened.
Therefore, the method can prevent the interior of the electric pile 1 from icing for a long time, and prolong the service life of the membrane electrode; meanwhile, the low-temperature starting time is shortened, and the energy consumption is reduced, so that the adaptability of the fuel cell stack 1 under the low-temperature condition is improved.
Example 2
As shown in fig. 2, a method for storing and rapidly starting a fuel cell stack 1 under low temperature conditions includes the following steps:
s1, adding a phase change material into a packaging shell of the galvanic pile, and arranging the galvanic pile with the packaging shell on a vehicle;
that is to say, the organic phase change material combined with the expanded graphite is added in the packaging shell, so that the phase change material is well wrapped in the expanded graphite, the leakage phenomenon cannot occur in the heat treatment process, the adsorption effect is good, the stable solid shape can be kept before and after phase change, and the packaging shell has no flowability.
Specifically, a first phase change material is filled in the lower plate 11 of the package housing, and the first phase change material is a decanol-palmitic acid/expanded graphite ternary composite organic phase change material. The preparation process is approximately as follows: firstly, decyl alcohol and palmitic acid are mixed according to the mass ratio of 97.8: 2.2 to form a binary eutectic mixture, then mixing at 15: 1, adsorbing the graphite on expanded graphite to obtain the product; the upper plate 12 is filled with a second phase-change material which is a palmitic acid/expanded graphite composite phase-change energy storage material, and is prepared by taking palmitic acid as a matrix and expanded graphite as a reinforced heat transfer material and adsorbing molten liquid palmitic acid in a microporous structure of the expanded graphite. The proportion of the palmitic acid is 80wt%, the proportion of the expanded graphite is 20wt%, and the composite phase-change material can be subjected to melting/freezing thermal cycle for more than 3000 times.
And S2, loading an inert gas bottle 4 on the vehicle, and after the electric pile 1 is switched from the working state to the shutdown state, providing inert gas through the inert gas bottle 4 to purge the electric pile 1, wherein after the purging is finished, the inert gas stays in the electric pile 1.
That is to say, when the electric pile 1 is shut down, the electric pile 1 is purged immediately without cooling, and the residual moisture in most of the electric pile 1 is removed in a short time by means of the residual heat of the electric pile 1. In addition, after the purging is stopped, the low-pressure inert gas stays in the galvanic pile 1 for a long time, and the secondary purging is avoided after the startup.
Specifically, an inert gas bottle 4 is loaded on the vehicle, and a purging system is installed on the vehicle and used for controlling the inert gas bottle 4 to purge the galvanic pile 1. After the shutdown, the fuel supply pipeline and the air supply pipeline are switched to inert gas, the stack 1 is purged by the depressurized inert gas, the moisture in the membrane electrode is reduced, the hydrogen gas cavity and the air cavity of the stack 1 are filled with the inert gas, and after the purging is finished, the inert gas stays in the stack 1 for a long time.
Wherein the inert gas is nitrogen, and the vehicle-mounted nitrogen bottle adopts a 1L 15MPa specification. Further, the purge system includes a pressure reducing valve 42, a first solenoid valve 41, a second solenoid valve 26, a first control valve 45, a second control valve 44, a first three-way valve 43, a second three-way valve 31, a third three-way valve 21, a back pressure valve 37, a first flow sensor 32, a second flow sensor 22, a first pressure sensor 33, a second pressure sensor 23, a first humidity sensor 36, a second humidity sensor 25, a first temperature sensor 34, a second temperature sensor 35, and a third temperature sensor 24, the inert gas bottle 4, the first solenoid valve 41, the pressure reducing valve 42, and the first three-way valve 43 are connected in sequence, the first three-way valve 43 connects the first control valve 45 and the second control valve 44, the first control valve 45 connects the second three-way valve 31, the second three-way valve 31 is connected to an external air inlet line 3, and the second three-way valve 31 is connected to the first flow sensor 32, the first flow sensor 32 is connected to the first pressure sensor 33, the first pressure sensor 33 is connected to the first temperature sensor 34, the first temperature sensor 34 is connected to the cell stack 1, the second control valve 44 is connected to the third three-way valve 21, the third three-way valve 21 is connected to an external hydrogen inlet pipe 2, the third three-way valve 21 is connected to the second flow sensor 22, the second flow sensor 22 is connected to the second pressure sensor 23, the second pressure sensor 23 is connected to the cell stack 1, the second temperature sensor 35 is connected to the first humidity sensor 36, the first humidity sensor 36 is connected to the back pressure valve 37, and the third temperature sensor 24 is connected to the cell stack 1, and the third temperature sensor 24 is connected with the second humidity sensor 25, and the second humidity sensor 25 is connected with the second solenoid valve 26.
The specific operation is as follows: after a stop button of a cockpit is clicked, a switch of a nitrogen purging system is opened, the electromagnetic valve 41 starts to work, the pressure is controlled to be 10-50kPa through the pressure reducing valve 42, and the nitrogen purging flow is as follows: the air circuit purging flow is adjusted to 9L/min, the hydrogen circuit purging flow is adjusted to 3L/min, and the cathode and anode chambers of the galvanic pile 1 are purged. And (3) monitoring the temperature and the humidity of outlet gas in real time by using outlet temperature and humidity sensors, and when the temperature of the outlet inert gas is lower than 40 ℃ and the relative humidity is lower than 20%, closing a purging system electromagnetic valve 41, and simultaneously closing a back pressure valve 37 at the outlet of an air path and an electromagnetic valve 26 at the outlet of a hydrogen path, so that the nitrogen stays in the cell stack 1 for a long time.
That is, the inert gas cylinder 4, the first solenoid valve 41, the pressure reducing valve 42, and the first three-way valve 43 are connected in this order, and then divided into two paths: one path of the gas flow is sequentially connected with a first control valve 45, a second three-way valve 31, a first flow sensor 32, a first pressure sensor 33 and a first temperature sensor 34, enters the galvanic pile 1 from an end plate of the galvanic pile 1, and then purges a cathode chamber of the galvanic pile 1; the other path is connected with a second control valve 44, a third three-way valve 21, a second flow sensor 22 and a second pressure sensor 23 in sequence, enters the electric pile 1 from the end plate of the electric pile 1, and then purges the anode chamber of the electric pile 1. The purge gas is discharged from the cathode chamber of the stack 1 through the second temperature sensor 35, the first humidity sensor 36 and the back pressure valve 37 in sequence, discharged from the anode chamber of the stack 1 through the third temperature sensor 24, the second humidity sensor 25 and the second electromagnetic valve 26 in sequence, and the water content in the stack 1 is indirectly judged by monitoring the gas temperature and humidity of the air outlet and the hydrogen outlet.
When the temperatures measured by the second temperature sensor 35 and the third temperature sensor 24 are lower than 40 ℃, and when the humidity measured by the first humidity sensor 36 and the second humidity sensor 25 is lower than 20%, the first electromagnetic valve 41, the second electromagnetic valve 26 and the back pressure valve 37 are closed, so that the nitrogen gas stays in the cell stack 1 for a long time.
S3, when the environment temperature is low, the phase change material changes phase with the reduction of the temperature around the galvanic pile in the shutdown process, latent heat is released to preserve the temperature of the galvanic pile, when the galvanic pile 1 needs to be started under the low temperature condition, the phase change material is triggered to change phase to directly heat the galvanic pile 1, so that the galvanic pile 1 can be quickly started under the low temperature condition to enter a normal working state, and the low temperature condition is-30-0 ℃.
That is, when the stack 1 operates normally, the phase change material absorbs heat and undergoes phase change; when the environmental temperature is lower, along with the gradual reduction of the temperature around 1 of shut down process galvanic pile, the phase change material takes place reverse phase transition, releases the heat and gives the galvanic pile heating heat preservation, makes the galvanic pile can be for a long time in low temperature condition storage and not take place to freeze. When the low-temperature starting is carried out, the phase change material 2 added into the packaging shell of the galvanic pile 1 generates phase change to release heat, so that the galvanic pile 1 is directly heated, the efficiency and the utilization rate of heat are improved, the consumption of extra heat is reduced, and the low-temperature starting time is shortened. By starting the phase change trigger, the phase change material is heated to the phase change temperature through temperature compensation, so that the galvanic pile 1 is heated. The phase change trigger is a thermistor. That is, the phase change material for heating needs to be triggered using a phase change trigger, while the phase change material for heat preservation does not. When the reactor is started at a low temperature, firstly, the thermistor is started, the temperature of the phase-change material is raised to the phase-change temperature through temperature compensation, the heating is stopped after the palmitic acid is changed from the solid phase to the liquid phase, then the palmitic acid is changed from the liquid phase to the solid phase again due to the external low-temperature environment, and a large amount of heat is released, so that the reactor 1 is heated; after the electric pile 1 works normally, the palmitic acid keeps a liquid phase for a long time, and when the temperature of the electric pile 1 is reduced to below 60 ℃ after the electric pile is stopped, the palmitic acid is changed from the liquid phase to a solid phase again, so that the phase change process is controllable.
Therefore, the method can prevent the interior of the electric pile 1 from icing for a long time, and prolong the service life of the membrane electrode; meanwhile, the low-temperature starting time is shortened, and the energy consumption is reduced, so that the adaptability of the fuel cell stack 1 under the low-temperature condition is improved.
In one embodiment, a fuel cell stack 1 with an output of 25kW is selected, the package size is 247 x 420 x 104, the weight is 14kg, a graphite bipolar plate is used, the stack 1 has 90 sections, the specific heat capacity of the graphite bipolar plate is 710J/(kg.k), the specific heat capacity of the membrane electrode is 864J/(kg.k), the specific heat capacity of the collector plate is 390J/(kg.k), and the specific heat capacity of the end plate is 480J/(kg.k).
(1) When the low-temperature environment temperature is-10 ℃, the temperature of the galvanic pile 1 needs to be kept at 0 ℃, and the required heat Q is as follows:
the latent heat of phase change of the decanol-palmitic acid/expanded graphite is 193.9J/g, and the mass M of the phase change material is required to be:
(2) when the low-temperature start-up is carried out, the temperature of the galvanic pile 1 needs to be increased from 0 ℃ to 20 ℃ (normal temperature), and the required heat Q is as follows:
and the latent heat of phase change of the heating palmitic acid/expanded graphite is 148J/g, the mass M of the phase change material is required to be as follows:
therefore, the phase change material is used for directly heating the electric pile 1, compared with the traditional phase change material, the quantity of the phase change material required when the same quantity of heat is released is less, and the volume of the whole fuel cell can be smaller because the phase change material is arranged in the packaging shell.
In one embodiment, a fuel cell stack 1 having an output power of 25kW is selected,
(1) when the low-temperature environment temperature is-30 ℃, the temperature of the galvanic pile 1 needs to be kept at 0 ℃, and the required heat Q is as follows:
and the latent heat of phase change of the decanol-palmitic acid/expanded graphite for heat preservation is 193.9J/g, the mass M of the phase change material is required to be:
(2) when starting at low temperature, the temperature of the electric pile 1 needs to be increased from 0 ℃ to 20 ℃ (normal temperature), and the required phase change material amount is still 1.40 kg.
Specifically, C is the specific heat capacity of the galvanic pile, m is the mass of the galvanic pile, delta t is the temperature difference, namely the internal temperature of the galvanic pile minus the ambient temperature,is the latent heat of phase change of the phase change material.
It can be seen through the comparison, along with the reduction of vehicle daily operating mode ambient temperature, only need increase phase change material at the loading of galvanic pile encapsulation shell, on guaranteeing that cost increase is little, and volume change is obscure basis, alright realize that the fuel cell galvanic pile stores under the low temperature condition for a long time not freeze and the effect of quick start.
In summary, the above embodiments are not intended to be limiting embodiments of the present invention, and modifications and equivalent variations made by those skilled in the art based on the spirit of the present invention are within the technical scope of the present invention.
Claims (7)
1. A method for storing and quickly starting a fuel cell stack under low temperature conditions is characterized by comprising the following specific steps:
s1, adding a phase change material into a packaging shell of the galvanic pile, arranging the galvanic pile with the packaging shell on a vehicle, wherein the packaging shell comprises an upper plate, a lower plate, a left sealing plate and a right sealing plate, two ends of the galvanic pile are respectively provided with an end plate, one side of the upper plate is connected with one side of the lower plate through the left sealing plate, the other side of the upper plate is connected with the other side of the lower plate through the right sealing plate, the upper plate, the lower plate, the left sealing plate, the right sealing plate and the two end plates form a closed space, the galvanic pile is positioned in the closed space, the upper plate and the lower plate are double-layer plates, the phase change material comprises a first phase change material and a second phase change material, the first phase change material is arranged in the lower plate, the second phase change material is arranged in the upper plate, the inner layer of the upper plate and the inner layer of the lower plate are both heat-insulating layers, the first phase-change material is a decanol-palmitic acid/expanded graphite ternary composite organic phase-change material, the phase-change temperature of the first phase-change material is 2.7 ℃, the phase-change latent heat is 193.9J/g, and the mass ratio of decanol to palmitic acid in the first phase-change material is 97.8: 2.2, the second phase change material is a palmitic acid/expanded graphite composite organic phase change energy storage material, the phase change temperature is 60.8 ℃, the latent heat of phase change is 148J/g, and the ratio of the palmitic acid to the expanded graphite in the second phase change material is 80wt% and 20 wt%;
s2, loading an inert gas bottle on the vehicle, and after the galvanic pile is switched from the working state to the shutdown state, providing inert gas through the inert gas bottle to purge the galvanic pile, wherein after purging is finished, the inert gas stays in the galvanic pile;
s3, when the environment temperature is lower, the phase change material changes phase with the decrease of the temperature around the galvanic pile in the shutdown process, and releases latent heat to preserve the heat of the galvanic pile; when the galvanic pile needs to be started under a low-temperature condition, the galvanic pile is directly heated by triggering the phase-change material to carry out phase change, so that the galvanic pile can be quickly started under the low-temperature condition of-30 ℃ to 0 ℃, the phase-change material is heated to the phase-change temperature through temperature compensation by starting the phase-change trigger, and then the phase-change latent heat is controllably released, so that the galvanic pile is heated.
2. The method for storage and rapid start-up of a fuel cell stack under cryogenic conditions according to claim 1, wherein: the heat-insulating layer is made of hard polyurethane foam.
3. The method for storage and rapid start-up of a fuel cell stack under cryogenic conditions according to claim 1, wherein: in the step S2, a purge system is installed on the vehicle, and the purge system is used for controlling the inert gas bottle to purge the electric pile.
4. The method for storage and rapid start-up of a fuel cell stack under cryogenic conditions according to claim 3, wherein: the purging system comprises a pressure reducing valve, a first electromagnetic valve, a second electromagnetic valve, a first control valve, a second control valve, a first three-way valve, a second three-way valve, a third three-way valve, a back pressure valve, a first flow sensor, a second flow sensor, a first pressure sensor, a second pressure sensor, a first humidity sensor, a second humidity sensor, a first temperature sensor, a second temperature sensor and a third temperature sensor, wherein the inert gas bottle, the first electromagnetic valve, the pressure reducing valve and the first three-way valve are sequentially connected, the first three-way valve is connected with the first control valve and the second control valve, the first control valve is connected with the second three-way valve, the second three-way valve is connected with an external air inlet pipeline, the second three-way valve is connected with the first flow sensor, and the first flow sensor is connected with the first pressure sensor, the first pressure sensor is connected with the first temperature sensor, and the first temperature sensor is connected with the galvanic pile; the second control valve is connected the third three-way valve, the third three-way valve is connected with outside hydrogen inlet pipeline, just the third three-way valve is connected the second flow sensor, the second flow sensor is connected the second pressure sensor, the second pressure sensor with the pile is connected, the second temperature sensor with the pile is connected, just the second temperature sensor with first humidity transducer is connected, first humidity transducer with the back pressure valve is connected, the third temperature sensor with the pile is connected, just the third temperature sensor with the second humidity sensor is connected, the second humidity sensor with the second solenoid valve is connected.
5. The method for storage and rapid start-up of a fuel cell stack under cryogenic conditions according to claim 1, wherein: the inert gas is nitrogen.
6. The method for storage and rapid start-up of a fuel cell stack according to claim 4, wherein: in the step S2, when the temperatures measured by the second and third temperature sensors are lower than 40 ℃, and when the humidities measured by the first and second humidity sensors are lower than 20%, the first solenoid valve, the second solenoid valve, and the back pressure valve are closed.
7. The method for storage and rapid start-up of a fuel cell stack under cryogenic conditions according to claim 1, wherein: the phase change trigger is a thermistor.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111139906.8A CN113594504B (en) | 2021-09-28 | 2021-09-28 | Method for storing and quickly starting fuel cell stack under low-temperature condition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111139906.8A CN113594504B (en) | 2021-09-28 | 2021-09-28 | Method for storing and quickly starting fuel cell stack under low-temperature condition |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113594504A CN113594504A (en) | 2021-11-02 |
CN113594504B true CN113594504B (en) | 2022-03-22 |
Family
ID=78242200
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111139906.8A Active CN113594504B (en) | 2021-09-28 | 2021-09-28 | Method for storing and quickly starting fuel cell stack under low-temperature condition |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113594504B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114023994B (en) * | 2021-11-09 | 2023-07-07 | 天津大学 | Concatenation formula fuel cell phase transition insulation can |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006185657A (en) * | 2004-12-27 | 2006-07-13 | Toyota Motor Corp | Warming-up device of fuel cell stack |
CN103992772A (en) * | 2014-05-23 | 2014-08-20 | 西南交通大学 | Composite phase change energy storage material and preparation method thereof |
CN109888332A (en) * | 2019-02-28 | 2019-06-14 | 吉利汽车研究院(宁波)有限公司 | A kind of fuel cell heat management system and thermal management algorithm |
CN111082185A (en) * | 2019-12-09 | 2020-04-28 | 全球能源互联网欧洲研究院 | Composite binary phase change material and application thereof in battery thermal management system |
CN113299946A (en) * | 2021-05-17 | 2021-08-24 | 北京格睿能源科技有限公司 | Thermal management method and device for shutdown condition of fuel cell |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102485321B1 (en) * | 2016-10-26 | 2023-01-06 | 현대자동차주식회사 | Thermal management system for fuel cell vehicle and control method thereof |
US20180219237A1 (en) * | 2017-01-27 | 2018-08-02 | Ford Motor Company | Fuel Cell Freeze Protection Device and System |
-
2021
- 2021-09-28 CN CN202111139906.8A patent/CN113594504B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006185657A (en) * | 2004-12-27 | 2006-07-13 | Toyota Motor Corp | Warming-up device of fuel cell stack |
CN103992772A (en) * | 2014-05-23 | 2014-08-20 | 西南交通大学 | Composite phase change energy storage material and preparation method thereof |
CN109888332A (en) * | 2019-02-28 | 2019-06-14 | 吉利汽车研究院(宁波)有限公司 | A kind of fuel cell heat management system and thermal management algorithm |
CN111082185A (en) * | 2019-12-09 | 2020-04-28 | 全球能源互联网欧洲研究院 | Composite binary phase change material and application thereof in battery thermal management system |
CN113299946A (en) * | 2021-05-17 | 2021-08-24 | 北京格睿能源科技有限公司 | Thermal management method and device for shutdown condition of fuel cell |
Also Published As
Publication number | Publication date |
---|---|
CN113594504A (en) | 2021-11-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1672727B1 (en) | Methods for improving the cold starting capability of an electrochemical fuel cell | |
US20050048338A1 (en) | Polymer electrolyte fuel cell system and operation method thereof | |
CN105702979A (en) | Starting method for fuel cell stack in environment below zero | |
CN102386430B (en) | Proton exchange membrane fuel cell system with low-temperature storage and starting functions | |
CN105244519A (en) | Metal hydride hydrogen storage and fuel cell combination system | |
JP2009054404A (en) | Fuel cell system | |
JP2002543566A (en) | Freeze-resistant fuel cell system and method | |
JP3883125B2 (en) | Fuel cell system and method for stopping fuel cell system | |
KR100994509B1 (en) | Fuel cell stack including Phase Change Meterials | |
CN101170185A (en) | A gas water cleaning method of proton exchange film fuel battery | |
CN113594504B (en) | Method for storing and quickly starting fuel cell stack under low-temperature condition | |
US7482085B2 (en) | Apparatus for improving the cold starting capability of an electrochemical fuel cell | |
CN112701317A (en) | Vehicle fuel cell air system with cold start function and control method thereof | |
JPS6326962A (en) | Stop and storing method for fuel cell | |
JP2000164232A (en) | Solid high molecular fuel cell system | |
KR100802749B1 (en) | A fuel cell system for a vehicle | |
CN114122467B (en) | Hydrogen energy power supply device and method for hydrogen supply by hydrolysis of hydrogen storage material and normal low-temperature self-starting | |
US7534511B2 (en) | Thermal control of fuel cell for improved cold start | |
US8067121B2 (en) | Fuel cell system which can be used in a mobile manner with an adsorption accumulator | |
CN211088406U (en) | Vehicle fuel cell air system with cold start function | |
JP2013541148A (en) | Method and apparatus for preventing oxidation of anode | |
CN110911715A (en) | Cold start method for fuel cell stack | |
JP2010153067A (en) | Fuel cell system | |
JP3671914B2 (en) | Thermal insulation structure of pure water tank | |
CN220829989U (en) | Cold starting device for fuel cell |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
TA01 | Transfer of patent application right | ||
TA01 | Transfer of patent application right |
Effective date of registration: 20220225 Address after: 518000 101, No.1 Workshop, xiongtao science and Technology Park, Shuitou community, Dapeng street, Dapeng New District, Shenzhen City, Guangdong Province Applicant after: Shenzhen hurui Fuel Cell Technology Co.,Ltd. Address before: 510000 Room 102, building 1, No. 133, Buling Road, Huangpu District, Guangzhou, Guangdong Applicant before: Guangzhou xiongtao Hydrogen Technology Co.,Ltd. |
|
GR01 | Patent grant | ||
GR01 | Patent grant |