CN114361528B - Method and system for effectively improving low-temperature starting capability of proton exchange membrane fuel cell - Google Patents
Method and system for effectively improving low-temperature starting capability of proton exchange membrane fuel cell Download PDFInfo
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- CN114361528B CN114361528B CN202011093673.8A CN202011093673A CN114361528B CN 114361528 B CN114361528 B CN 114361528B CN 202011093673 A CN202011093673 A CN 202011093673A CN 114361528 B CN114361528 B CN 114361528B
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- 239000000446 fuel Substances 0.000 title claims abstract description 115
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000012528 membrane Substances 0.000 title abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 220
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims description 3
- 238000012544 monitoring process Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 239000003054 catalyst Substances 0.000 description 9
- 238000009529 body temperature measurement Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000110 cooling liquid Substances 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
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- 238000007254 oxidation reaction Methods 0.000 description 3
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- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
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- 239000000463 material Substances 0.000 description 2
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- 229910052697 platinum Inorganic materials 0.000 description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
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- 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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Abstract
The invention relates to the field of proton exchange membrane fuel cells, and discloses a method and a system for effectively improving the low-temperature starting capability of a proton exchange membrane fuel cell, wherein the method comprises the steps of alternately introducing mixed gas of an anode and a cathode from an air inlet and an air outlet of the fuel cell; the air inlet and the air outlet are an anode air inlet and an anode air outlet at the same time, or the air inlet and the air outlet are a cathode air inlet and a cathode air outlet at the same time, or the air inlet is an anode air inlet and a cathode air inlet at the same time, and the air outlet is a cathode air inlet and a cathode air outlet at the same time. The fuel cell pile system is added with a forward gas supply pipeline and a reverse gas supply pipeline, so that the mixed gas of hydrogen and air is alternately introduced into the outlet and the inlet of the fuel cell or the fuel cell pile gas cavity, and each part of the pile is heated uniformly and quickly to reach the appointed starting temperature.
Description
Technical Field
The invention relates to the technical field of proton exchange membrane fuel cells, in particular to a method for effectively improving the low-temperature starting capability of a proton exchange membrane fuel cell.
Background
The proton exchange membrane fuel cell is more and more concerned because of the characteristics of high efficiency, low noise, no pollution and the like, and particularly has wide application prospect in the field of carrier power sources. The proton exchange membrane used in the proton exchange membrane fuel cell widely used in the current stage is a perfluorosulfonic acid membrane, and the membrane needs to be fully wetted by water under normal working conditions to improve proton conductivity, which causes no small difficulty in low-temperature cold start of the fuel cell, because water can be frozen below the freezing point of the fuel cell, and the water can possibly cover the active site of the catalyst or block a gas transmission pore canal, so that the cell is stopped or even damaged. How to quickly raise the temperature of the cell core above the freezing point has become an important issue that restricts the rapid commercialization of fuel cells, and low-temperature start-up capability has also become one of the important indicators of fuel cells.
In order to improve the low-temperature starting capability of the proton exchange membrane fuel cell, in the prior art: the patent application CN101170187A proposes a hydrogen pump principle, which quantitatively transfers the hydrogen on the anode side of the fuel cell to the cathode, thereby enabling the hydrogen to react with oxygen, rapidly increasing the internal temperature of the cell and realizing the starting at-5 to-20 ℃, wherein the current density of the hydrogen pump is 200-600mA/cm 2 The temperature of the galvanic pile can be raised to 0 ℃ for 120s at the temperature of minus 20 ℃. After reaching zero degree, the electric pile normally loads output energy. The patent application CN102751521B utilizes the compression heat release of an air compressor, circulates the tail gas at the air side back to the compressor to heat the air again, and further improves the temperature of the electric pile to realize the temperature rise of the electric pile from minus 10 ℃ to 0 ℃ within 300 seconds, and the patent application requires a secondary battery to start the air compressor, and cannot start by the method if the SOC of the secondary battery is lower
US20120118878A1 incorporates an electrical heating unit in the fuel cell system to heat the coolant, causing the coolant to indirectly heat the stack to a temperature threshold. The patent requires resistance wires and the like to raise the temperature of the cooling liquid, and the temperature rise is slower.
Chinese patent CN106558713B and US20070224462A1 employ a hydrogen catalytic oxidation heat exchanger added to a fuel cell stack system, and the heat exchanger is used to heat cooling water, thereby allowing the cooling water to indirectly warm up the stack. The above patent application places the reaction site of catalytic oxidation in the air of hydrogen outside the electric pile, develops a module alone to provide a reaction site, and the generated heat needs to reach the electric pile through cooling water heat exchange, the heating is not direct, and the system is complex.
The fuel cell system of Chinese patent CN110103777A comprises two mutually independent fuel cell stacks, wherein one fuel cell stack is heated by circulating cooling liquid to enable the core temperature to reach a set threshold (-10-0 ℃), and the other fuel cell stack is heated by the fuel cell stack, so that the method has single application scene and needs larger space, and is generally used for high-power and large-internal space scenes of engineering machinery and the like
Chinese patent CN108832158A adopts the mode of introducing hydrogen and oxygen after mixing and then anode, letting anode tail gas flow back to cathode to raise the temperature rising rate, but this method is easy to leave oxygen at anode, and air exists at both sides of fuel cell, and long-term use can make cell decay due to hydrogen air interface phenomenon, and this method temperature rising is not uniform.
Disclosure of Invention
The invention aims to provide a method and a system for effectively improving the low-temperature starting capability of a proton exchange membrane fuel cell, which are used for relieving the temperature non-uniformity of the temperature rise of the direct reaction of hydrogen and air mixture in an air cavity.
In one aspect, the invention provides a method for starting a fuel cell at a low temperature, which comprises the following steps: alternately introducing the mixed gas of the anode and the cathode from the gas inlet and the gas outlet of the fuel cell; the air inlet and the air outlet are an anode air inlet and an anode air outlet at the same time, or the air inlet and the air outlet are a cathode air inlet and a cathode air outlet at the same time, or the air inlet is an anode air inlet and a cathode air inlet at the same time, and the air outlet is a cathode air inlet and a cathode air outlet at the same time.
Based on the above, preferably, the method comprises the steps of:
(1) The mixed gas takes a certain time t 1 Alternately introducing an air inlet and an air outlet;
(2) Monitoring the temperature of the air inlet, middle and air outlet positions of the fuel cell stack;
(3) The temperatures of the three positions of the fuel cell stack reach a certain value T 1 When the mixed gas is stopped entering, the fuel electricity is realizedThe cell was operating normally.
Based on the above scheme, preferably, the mixed gas is hydrogen and air; the mole fraction of the hydrogen accounts for 76-95% or 1-3% of the mixed gas.
Based on the scheme, the flow rate of the mixed gas is preferably 2-20L/min for each single cell in the fuel cell stack.
Based on the above scheme, preferably, the low temperature is-50 ℃ to-20 ℃.
Based on the above scheme, preferably T 1 Is at the temperature of-15 ℃ to 15 ℃; alternating air supply time t of forward and reverse air supply pipeline 1 The specific time is determined by the gas speed, the mixed gas proportion, the initial temperature of the fuel cell or the fuel cell stack, and the performance of the fuel single cell or the fuel cell stack, and is 2 to 120s, preferably 2 to 60 s. Thereby leading each part of the electric pile to be heated evenly and quickly and reaching the preset value T quickly 1 。
In another aspect, the present invention provides a fuel cell low temperature start-up system comprising a fuel cell, an anode gas input line and output line, a cathode gas input line and output line, a forward gas feed line and a reverse gas feed line; the positive gas supply pipeline is used for introducing the mixed gas of the anode and the cathode to the gas inlet of the fuel cell; the reverse gas supply pipeline is used for introducing the mixed gas of the anode and the cathode to the gas outlet of the fuel cell. The positive direction and the reverse direction are opposite, so long as the mixed gas of the anode gas and the cathode gas is ensured to alternately enter the corresponding air inlet and the air outlet through the positive air supply pipeline and the reverse air supply pipeline.
Based on the above-described aspect, preferably, the forward gas supply line is in communication with the fuel cell anode gas input and output line, and the reverse gas supply line is in communication with the fuel cell anode gas input and output line; and/or the forward gas supply pipeline is communicated with the cathode gas input and output pipeline of the fuel cell, and the reverse gas supply pipeline is communicated with the cathode gas input and output pipeline of the fuel cell.
Based on the above scheme, preferably, when the forward and reverse air supply pipeline is communicated with the cathode air input and output pipeline of the fuel cell, and the reverse air supply pipeline is communicated with the cathode air input and output pipeline of the fuel cell, the system is specifically as follows:
the anode gas inlet of the fuel cell is communicated with the anode gas input pipeline; the anode gas outlet of the fuel cell is communicated with the anode gas output pipeline;
a valve II is arranged at one end, close to the anode gas inlet, of the anode gas input pipeline, and a valve I is arranged at one end, close to the anode gas outlet, of the anode gas output pipeline;
the cathode air inlet of the fuel cell is communicated with the cathode input pipeline; the cathode gas outlet of the fuel cell is communicated with the cathode gas output pipeline;
the cathode gas input pipeline is provided with a gas mixing point, a valve eleven and a valve IV, wherein the gas mixing point is positioned at one end far away from the cathode gas inlet and is communicated with the anode gas input pipeline through a pipeline provided with a valve IV, and the connecting point is positioned at one end far away from the anode gas inlet; the valve IV is positioned at one end close to the cathode air inlet, and the valve eleven is positioned between the air mixing point and the valve IV;
the cathode gas output pipeline is provided with a valve III and a valve twelve, the valve III is positioned at one end close to the cathode gas outlet, and the valve twelve is positioned at one end far away from the cathode gas outlet;
the positive air supply pipeline comprises a valve seven and a valve ten, the valve ten is connected with the valve eleven in parallel through a pipeline, and the valve seven is connected with the valve twelve in parallel through a pipeline;
the reverse air supply pipeline comprises a valve six and a valve nine, one end of the valve nine is communicated with the air mixing point, the other end of the valve nine is communicated with the cathode air outlet through the valve three, one end of the valve six is communicated with the cathode air inlet through the valve four, and the other end of the valve six is communicated with the outlet of the cathode air output pipeline.
The positive gas supply pipeline is used for supplying mixed gas to a cathode gas inlet of the fuel cell, and the gas flow path is as follows: anode gas and cathode gas are mixed by a gas mixing point, sequentially pass through a valve ten, a valve four, a cathode air inlet, a cathode air outlet and a valve seven, and finally are discharged through a cathode tail.
The reverse gas supply system is used for supplying mixed gas to the anode gas outlet of the fuel cell, and the gas flow path is as follows: anode gas and cathode gas are mixed by a gas mixing point, sequentially pass through a valve nine, a valve three, a cathode gas outlet, a cathode gas inlet, a valve four and a valve six, and finally are discharged through a cathode tail.
Based on the above scheme, preferably, any one of the control modes of the valve is electromagnetic control, manual control or pneumatic control; any valve is a normal pressure two-position two-way valve, and in practice, the method for changing the fluid flow direction is quite many, and the technical scheme provided by the invention is not limited to the valve group of the four valves, and the operation of exchanging the air supply direction can be realized by using three two-position three-way valves or one two-position four-way valve.
The system is provided with a forward and reverse air supply pipeline; the forward and reverse air supply pipeline is connected with a cathode cavity or an anode cavity of the fuel cell stack; the forward gas supply pipeline is connected with the gas inlet of the proton exchange membrane fuel cell, and the reverse gas supply pipeline is connected with the gas outlet of the proton exchange membrane fuel cell; mixing hydrogen and air according to a certain proportion and then introducing the mixture into an air supply system; the mixed gas is used for a certain time t 1 Switching to a forward or reverse air supply pipeline; temperature sensors are respectively arranged at the air inlet, the middle and the air outlet of the fuel cell stack; the temperature of the three positions of the fuel cell stack reaches a certain value T 1 And stopping entering the mixed gas when the mixed gas is in the process.
The proton exchange membrane fuel cell refers to a fuel cell which utilizes a polymer film capable of transmitting protons to isolate a cathode and an anode, and the fuel cell can be a single fuel cell or a fuel cell stack formed by connecting a plurality of fuel cell sheets in series, and is called a fuel cell stack when the fuel cell stack is formed by connecting a plurality of fuel cell sheets in series.
The fuel cell stack should include a proton exchange membrane, a cathode and anode catalyst layer, a cathode and anode gas diffusion layer, a bipolar plate, a current collector plate, and an end plate.
The bipolar plate can be a composite plate or a metal bipolar plate and comprises a cathode flow channel, an anode flow channel and a cooling liquid flow channel.
The catalysts in the cathode catalyst layer are platinum-based catalysts and are mixed with proton exchange membrane materials.
The gas diffusion layer can be made of carbon paper or metal, wherein one side contacted with the catalyst layer is coated with microporous material, and the material consists of carbon powder and PTFE.
The mixed gas is required to be finally introduced into the cathode air cavity or the anode air cavity or simultaneously introduced into the cathode air cavity and the anode air cavity.
The forward and reverse air supply pipeline is characterized in that:
a) The forward and reverse gas feed lines may be mounted at the cathode inlet front end, the cathode outlet rear end, and/or the anode inlet front end, the anode inlet rear end.
b) The forward and reverse gas supply pipelines are used for changing the gas flow direction, namely, the gas flow direction in the cathode gas cavity or the anode gas cavity of the fuel cell or the fuel cell stack can be changed after electric control, manual control or pneumatic control.
c) The system can be composed of four electromagnetic valves or manual valves or pneumatic valves, can also be composed of three normal pressure two-position three-way electromagnetic valves or manual valves or pneumatic valves, and can also be composed of one normal pressure two-position four-way electromagnetic valve or manual valve or pneumatic valve.
The method of introducing mixed gas of hydrogen and air into the fuel cell stack cavity is utilized to quickly raise the temperature of the fuel cell to a starting node which can be a certain temperature of-15 ℃ to 15 ℃, and the temperature is determined according to different stack performances, environments and other factors. The fuel cell system is added with a forward and reverse gas supply pipeline, so that the mixed gas is switched between the gas inlet and the gas outlet every 2-60 s, and the specific time interval is determined by the gas speed of the mixed gas, the proportion of the mixed gas, the initial temperature of the fuel cell stack and the performance of the fuel cell stack. When the gas supply system comprises the forward and reverse gas supply pipelines, the temperature of the whole fuel cell stack is uniformly increased, and the condition of overlarge temperature difference among all temperature measuring points can not occur.
Advantageous effects
(1) The method and the system alternately feed gas to react at the two ends of the fuel cell stack, so that the temperature of the whole fuel cell stack is uniformly increased, and the condition of overlarge temperature difference among all temperature measuring points can not occur. And the integral temperature rising speed is high, and the requirement of quick cold start can be met.
(2) The invention realizes low-temperature start through the arrangement of simple pipelines and valves on the original air supply pipeline of the fuel cell, has simple system and changeable system structure, can be arranged only at the cathode air inlet and the cathode air outlet or only at the anode air inlet and the anode air outlet, and can also be arranged at the corresponding air inlet and outlet of the cathode and the anode at the same time.
(3) The forward and reverse air supply pipeline has smaller space, so that the invention has various application scenes, can be used for large-scale engineering machinery and can also be used for space sensitive scenes of passenger cars.
(4) The invention does not need the secondary battery to output a large amount of energy, and can be used under the condition of low SOC of the secondary battery.
(5) Tests show that the average temperature of all temperature measuring points in a pile body of the forward gas supply pipeline and the reverse gas supply pipeline is increased to reach 0 ℃ within 55s, wherein the temperature measuring point with the lowest temperature reaches 0 ℃ within 79s, and the variance of the temperature of each temperature measuring point in the fuel cell pile from the average temperature of the pile is not more than 5 in the whole heating process.
Drawings
FIG. 1 is a schematic diagram of a pile assembly and a temperature measurement point according to an embodiment of the present invention.
Fig. 2 is a schematic gas circuit diagram of a fuel cell stack system of a gas feed system according to an embodiment of the present invention.
Fig. 3 is a temperature rise curve of each temperature measurement point of the fuel cell stack according to the embodiment of the present invention.
Fig. 4 is a graph showing the temperature rise at each temperature measurement point of a fuel cell stack without using a forward and reverse air feed line.
Fig. 5 is a variance comparison graph calculated from the temperature rise curves of the respective temperature measurement points of the fuel cell stack according to the embodiment of the present invention and the temperature rise curves of the respective temperature measurement points of the fuel cell stack without using the forward and reverse air supply lines.
In the figure, 101 is a cathode current collector, 105 is an anode current collector, 102 is a bipolar plate, 104 is a temperature measuring point of the five batteries, which are respectively positioned at a cathode outlet of a first section, a cathode inlet of a second section, a cathode middle of a third section, a cathode outlet of a fourth section and a cathode inlet of a fifth section; 1 is valve one (anode outlet valve); 2 is valve two (anode inlet valve); 3 is valve three (cathode outlet valve); 4 is valve four (cathode inlet valve); 5 is valve five (gas mixing valve); 6 is a valve six (a reverse air supply pipeline valve); 7 is valve seven (positive air supply pipeline valve); 8 is a gas mixing point; 9 is valve nine (reverse air supply pipeline valve); 10 is valve ten (positive air supply pipeline valve); 11 is valve eleven (a valve isolated from a forward and reverse air supply pipeline); 12 is a valve twelve (a valve isolated from a forward and reverse air supply pipeline); 13 is an anode tail row; 14 is the anode gas supply end; 15 is the cathode gas supply end; 16 is the cathode tail row and 17 is the fuel cell stack.
Detailed Description
Example 1
In order to describe the working flow of the whole system conveniently, the invention will be further described with reference to the accompanying drawings and specific embodiments, wherein the environmental temperature is-30 ℃, the fuel cell stack is a fuel cell stack formed by 5 sheet-shaped fuel cells, the bipolar plate is made of metal stamping plates, the proton exchange membrane is made of perfluorosulfonic acid membrane, the cathode and anode catalysts are platinum-carbon composite catalysts, perfluorosulfonic acid is filled in the catalyst, and the platinum loading of the cathode is 0.4mg/cm respectively 2 Anode of 0.2mg/cm 2 。
Fig. 2 is a schematic gas circuit diagram of a fuel cell stack system incorporating a forward and reverse gas feed line, but it should be noted that this is only one application of the forward and reverse gas feed line, and it is not possible or exhaustive of all the implementations.
In this embodiment, four valves, namely, a valve six 6, a valve seven 7, a valve nine 9 and a valve ten 10, are adopted in the forward and reverse air supply pipeline, the valve six 6 and the valve nine 9 belong to a reverse air supply system, the valve seven 7 and the valve ten 10 are forward air supply systems, the systems are arranged at the front end of a cathode inlet and the rear end of a cathode outlet, pure hydrogen is introduced into an anode air supply end 14, compressed air is introduced into a cathode air supply end 15, and the flow rates of the hydrogen and the air are regulated by mass flow meters, and the valves used in this embodiment are all normal pressure two-position two-way valves.
The system provided in this embodiment is specifically installed as follows:
the anode gas inlet and the anode gas outlet of the fuel cell are respectively connected with an anode gas input pipeline and an anode gas output pipeline;
a valve II 2 is arranged at one end of the anode gas input pipeline, which is close to the anode gas inlet, and a valve I1 is arranged at one end of the anode gas output pipeline, which is close to the anode gas outlet;
the cathode air inlet and the air outlet of the fuel cell are respectively connected with a cathode air input pipeline and an cathode air output pipeline;
the cathode gas input pipeline is provided with a gas mixing point 8, a valve eleven 11 and a valve IV 4, the gas mixing point 8 is positioned at one end far away from the cathode gas inlet and is communicated with the anode gas input pipeline through a pipeline provided with a valve IV 5, and the connecting point is positioned at one end far away from the anode gas inlet; the valve IV 4 is positioned at one end close to the cathode air inlet, and the valve eleven 11 is positioned between the air mixing point 8 and the valve IV 4;
the cathode gas output pipeline is provided with a valve III 3 and a valve twelve 12, the valve III 3 is positioned at one end close to the cathode gas outlet, and the valve twelve 12 is positioned at one end far away from the cathode gas outlet;
the positive air supply pipeline comprises a valve seven 7 and a valve ten 10, the valve ten 10 is connected with a valve eleven 11 in parallel through a pipeline, and the valve seven 7 is connected with a valve twelve 12 in parallel through a pipeline;
the reverse air supply pipeline comprises a valve six 6 and a valve nine 9, one end of the valve nine 9 is communicated with the air mixing point 8, the other end of the valve nine is communicated with the cathode air outlet through a valve three 3, one end of the valve six 6 is communicated with the cathode air inlet through a valve four 4, and the other end of the valve six is communicated with the outlet of the cathode air output pipeline.
The positive gas supply pipeline is used for supplying mixed gas to a cathode gas inlet of the fuel cell, and the gas flow path is as follows: anode gas and cathode gas are mixed by a gas mixing point, sequentially pass through a valve ten, a valve four, a cathode air inlet, a cathode air outlet and a valve seven, and finally are discharged through a cathode tail.
The reverse gas supply system is used for supplying mixed gas to a cathode gas outlet of the fuel cell, and the gas flow path is as follows: anode gas and cathode gas are mixed by a gas mixing point, sequentially pass through a valve nine, a valve three, a cathode gas outlet, a cathode gas inlet, a valve four and a valve six, and finally are discharged through a cathode tail.
The working process of the system is as follows:
when the temperature sensor of the electric pile displays that the core temperature is below minus 10 ℃, a cold start program is triggered, at the moment, a gas mixing valve five 5 is opened, an anode inlet valve two 2 and an outlet valve one 1 are closed, hydrogen is mixed with compressed air introduced from a cathode gas supply end 15 at a gas mixing point 8 through the gas mixing valve five 5 to prepare to be introduced into the electric pile through a forward and reverse gas supply pipeline formed by a valve six 6, a valve seven 7, a valve nine 9 and a valve ten 10, the heat is quickly released by utilizing the catalytic oxidation reaction of the hydrogen and the oxygen, the temperature of the electric pile is quickly and uniformly increased, at the moment, a valve three 3 and a valve four 4 are in a normally open state, and a valve eleven 11 and a valve twelve 12 are in a closed state. In order to uniformly raise the temperature of the stack, it is necessary to switch the inflow position of the mixed gas between the gas inlet and the gas outlet of the cathode of the cell at intervals of time, in this embodiment, the switching time T 1 The flow rate of the mixed gas is 10s, and the flow rate of the mixed gas is 4L/min, wherein the volume fraction of the hydrogen is 80%.
The positive gas is fed from the valve four 4 and flows out from the valve three 3 at the beginning, at the moment, the valve seven 7 and the valve ten 10 in the positive and negative gas feeding pipeline are opened, the valve six 6 and the valve nine 9 are closed, at the moment, the mixed gas is sequentially discharged from the cathode tail row 16 after the valve ten 10, the valve four 4, the fuel cell stack 17, the valve three 3 and the valve seven 7.
Reverse gas supply after reversing is performed, namely, gas is introduced into the valve III 3 and flows out of the valve IV 4, the valve seven 7 and the valve ten 10 are closed during reversing, the valve six 6 and the valve nine 9 are opened, and at the moment, the mixed gas sequentially passes through the valve nine 9, the valve III 3, the fuel cell stack 17, the valve four 4 and the valve six 6, and finally is discharged from the cathode tail row 16.
The two states are cycled and repeated until the temperature of 5 temperature measuring points in the fuel cell stack reaches the starting temperature, the valve six 6, the valve seven 7, the valve nine 9 and the valve ten 10 are closed, and the valve eleven 11 and the valve twelve 12 are opened. And closing the mixing valve five 5, and opening the anode inlet valve two 2 and the anode outlet valve one 1. And then normally gas-loaded.
FIG. 3 shows the temperature measurement point data of the above embodiment, and it can be seen that the temperature rise is relatively uniform and rapid, the average temperature reaches 0℃at 55s, and the temperatures of the five temperature measurement points reach over 0℃at 79 s.
Comparative example 1
In contrast, the forward and reverse air supply pipelines are directly isolated, namely, the valve six 6, the valve seven 7, the valve nine 9 and the valve ten 10 are closed, the valve eleven 11 and the valve twelve 12 are opened, the valve two 2 is closed, the valve five 5 is opened, the hydrogen and the air are directly mixed, and the mixing proportion and the total air quantity are consistent with those of the embodiment, so that a temperature rise curve chart 4 is obtained.
In order to more intuitively compare the temperature uniformity difference of the two, a variance parameter is introduced, and the formula is as follows:
where σ is the variance, T i For the temperature of each temperature measuring point, n is the number of temperature measuring points and T Avg The average temperature of all the temperature measurement points.
The variance curves of the two are shown in fig. 5, so that the variance of the added forward and reverse gas supply pipelines is always lower than 10, the non-added variance is always higher, the variance is already close to 20 by 70s, and the effect of controlling the temperature uniformity of each node of the galvanic pile by the forward and reverse gas supply pipelines is obvious.
While the invention and its embodiments have been described above, it should be understood by those skilled in the art that the invention is not limited to the embodiments but encompasses modifications within the spirit and scope of the appended claims.
Claims (7)
1. A low-temperature starting system of a fuel cell, which is characterized by comprising the fuel cell, an anode gas input pipeline and an output pipeline, a cathode gas input pipeline and an output pipeline, a forward gas supply pipeline and a reverse gas supply pipeline; the positive gas supply pipeline is used for introducing the mixed gas of the anode and the cathode to the gas inlet of the fuel cell; the reverse gas supply pipeline is used for introducing the mixed gas of the anode and the cathode to the gas outlet of the fuel cell;
the positive gas supply pipeline is communicated with the cathode gas input and output pipeline of the fuel cell, and the negative gas supply pipeline is communicated with the cathode gas input and output pipeline of the fuel cell, and the system is specifically as follows:
the anode gas inlet of the fuel cell is communicated with the anode gas input pipeline; the anode gas outlet of the fuel cell is communicated with the anode gas output pipeline;
a valve II is arranged at one end, close to the anode gas inlet, of the anode gas input pipeline, and a valve I is arranged at one end, close to the anode gas outlet, of the anode gas output pipeline;
the cathode air inlet of the fuel cell is communicated with the cathode input pipeline; the cathode gas outlet of the fuel cell is communicated with the cathode gas output pipeline;
the cathode gas input pipeline is provided with a gas mixing point, a valve eleven and a valve IV, wherein the gas mixing point is positioned at one end far away from the cathode gas inlet and is communicated with the anode gas input pipeline through a pipeline provided with a valve IV, and the connecting point is positioned at one end far away from the anode gas inlet; the valve IV is positioned at one end close to the cathode air inlet, and the valve eleven is positioned between the air mixing point and the valve IV;
the cathode gas output pipeline is provided with a valve III and a valve twelve, the valve III is positioned at one end close to the cathode gas outlet, and the valve twelve is positioned at one end far away from the cathode gas outlet;
the positive air supply pipeline comprises a valve seven and a valve ten, the valve ten is connected with the valve eleven in parallel through a pipeline, and the valve seven is connected with the valve twelve in parallel through a pipeline;
the reverse air supply pipeline comprises a valve six and a valve nine, one end of the valve nine is communicated with an air mixing point, the other end of the valve nine is communicated with a cathode air outlet through a valve three, one end of the valve six is communicated with a cathode air inlet through a valve four, and the other end of the valve six is communicated with an outlet of a cathode air output pipeline;
the forward gas supply pipeline gas flow path is as follows: anode gas and cathode gas are mixed through a gas mixing point, sequentially pass through a valve ten, a valve four, a cathode gas inlet, a cathode gas outlet and a valve seven, and finally are discharged through a cathode tail;
the reverse gas supply system gas flow path is: anode gas and cathode gas are mixed by a gas mixing point, sequentially pass through a valve nine, a valve three, a cathode gas outlet, a cathode gas inlet, a valve four and a valve six, and finally are discharged through a cathode tail.
2. The system of claim 1, wherein the control of any of the valves is electromagnetic, manual or pneumatic; any valve is a normal pressure two-position two-way valve.
3. The system of claim 1, wherein the fuel cell has temperature sensors at respective inlet, intermediate, and outlet locations.
4. A method of low temperature start-up using the fuel cell low temperature system according to any one of claims 1 to 3, characterized in that the method is: alternately introducing a mixed gas of anode gas and cathode gas from a gas inlet and a gas outlet of the fuel cell; the air inlet and the air outlet are respectively an anode air inlet and an anode air outlet, or the air inlet and the air outlet are respectively a cathode air inlet and a cathode air outlet, or the air inlet is simultaneously an anode air inlet and a cathode air inlet, and the air outlet is simultaneously an anode air outlet and a cathode air outlet.
5. The method of cold start-up according to claim 4, characterized in that the method comprises the steps of:
(1) The mixed gas takes a certain time t 1 Alternately introducing an air inlet and an air outlet;
(2) Monitoring the temperatures of three positions of an air inlet, a middle air outlet and an air outlet of the fuel cell stack;
(3) The temperatures of the three positions of the fuel cell stack reach a certain value T 1 When the fuel cell is in a normal state, the fuel cell stops entering the mixed gas;
T 1 is at-15 to 15 ℃; t is t 1 2 to 120s.
6. The method for cold start-up according to claim 4, wherein the mixture is hydrogen and air; the hydrogen mole fraction accounts for 76-95% or 1-3% of the mixed gas; the flow rate of the mixed gas is 2-20L/min for each single cell in the fuel cell stack.
7. The cold start-up method of claim 4, wherein the low temperature is-50 ℃ to-20 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101170194A (en) * | 2006-10-27 | 2008-04-30 | 新源动力股份有限公司 | A method for proton exchange film fuel battery under zero degree |
| KR20110044476A (en) * | 2009-10-23 | 2011-04-29 | 현대자동차주식회사 | Cold starting device and method for fuel cell |
| CN108711630A (en) * | 2018-06-11 | 2018-10-26 | 中国科学院大连化学物理研究所 | The method started under one proton exchanging film fuel battery low-temperature condition |
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| US7179556B2 (en) * | 2001-08-10 | 2007-02-20 | Denso Corporation | Fuel cell system |
| KR100980926B1 (en) * | 2008-06-12 | 2010-09-07 | 현대자동차주식회사 | Method for reverse activation of fuel cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101170194A (en) * | 2006-10-27 | 2008-04-30 | 新源动力股份有限公司 | A method for proton exchange film fuel battery under zero degree |
| KR20110044476A (en) * | 2009-10-23 | 2011-04-29 | 현대자동차주식회사 | Cold starting device and method for fuel cell |
| CN108711630A (en) * | 2018-06-11 | 2018-10-26 | 中国科学院大连化学物理研究所 | The method started under one proton exchanging film fuel battery low-temperature condition |
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