CN115810774A - Rapid activation method of proton exchange membrane fuel cell stack - Google Patents
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Abstract
The invention discloses a rapid activation method of a proton exchange membrane fuel cell stack, which comprises the following steps: checking the air tightness of the galvanic pile; heating the galvanic pile, and introducing nitrogen to the anode and the cathode for purging; introducing hydrogen into the anode, introducing nitrogen into the cathode, wherein the pressure of the anode is greater than that of the cathode; the nitrogen of the cathode is switched to air; carrying out oxygen deficiency activation and quickly reducing platinum oxide; carrying out pulse current circulation activation, and recording a polarization curve 1; and repeating the oxygen deficiency activation and the cyclic volt-ampere pulse activation to obtain a plurality of polarization curves, and judging whether the voltage deviation between the new polarization curve and the previous polarization curve is less than 10mV to complete the activation of the galvanic pile. The invention can quickly reduce the oxide on the surface of the catalyst, improve the activity of the catalyst, improve the utilization rate of the catalyst, fully wet the proton exchange membrane and open the ion channel.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a rapid activation method of a proton exchange membrane fuel cell stack.
Background
With the pressure for coping with climate change increasing and the low-carbon transformation and acceleration of energy sources, the hydrogen energy has attracted attention in the world due to the advantages of cleanness, high efficiency and rich application scenes. Hydrogen energy is a key energy for realizing carbon neutralization strategy, and currently, hydrogen energy development route maps are established in a plurality of countries. Countries and regions in Europe and America make substantial progress in the development of the hydrogen energy industry through strategic leading, route planning, industry support policies and continuous investment. China already takes the hydrogen energy industry as a strategic emerging industry, issues a plurality of support policies from various aspects such as encouraging innovation and investment, awarding and preferential benefits, and all levels of local governments and enterprises actively develop industrial layout and project construction. The hydrogen fuel cell vehicle is a vehicle using hydrogen as an energy source and well replaces an internal combustion engine vehicle.
The proton exchange membrane fuel cell is a core component of a fuel cell vehicle, and is an electrochemical device which directly converts chemical energy of hydrogen into electric energy, heat energy and water after reaction. It is characterized by zero pollution and water discharge; the energy utilization rate is high. As long as there is sufficient fuel gas hydrogen and oxygen, continuous operation can be performed for a long time.
After the fuel cell stack assembly is complete, it cannot be used directly, and the initial activity of the fuel cell stack is low in the electrochemical reaction. Therefore, it is necessary to activate the stack to maximize initial performance. This process of galvanic stack activation, also known as "preconditioning" or "break-in", is the complete wetting of the proton exchange membrane by water, ensuring hydrogen ion channels; removing impurities in the polymer electrolyte membrane or the electrode to improve ionic conductivity; reducing platinum oxide to improve catalytic activity; a good three-phase reaction interface is established, so that the fuel cell stack can exert the best working state and performance.
At present, the rapid activation of the fuel cell stack is generally realized by introducing humidified nitrogen for pre-activation and then enabling the fuel cell stack to be under a large current for a long time. However, this approach has disadvantages: the activation method needs longer time and consumes larger amount of hydrogen, which affects mass production of fuel cell stacks in later period. Therefore, there is a need for an activation process that can increase the activation time of a fuel cell stack while reducing the amount of hydrogen used for activation, in preparation for mass production of fuel cell vehicles.
Chinese patent CN202010884289.3 discloses a proton exchange membrane fuel cell activation method and device, the method comprises: before activating the proton exchange membrane fuel cell each time, carrying out polarization test on the proton exchange membrane fuel cell to obtain the maximum current density of the proton exchange membrane fuel cell; setting the maximum current density of the proton exchange membrane fuel cell as the current peak value of the activation pulse current, and setting the pulse period of the activation pulse current and the duty ratio of the current peak value; the patent can increase the activation speed of the proton exchange membrane fuel cell and reduce the activation time according to the activation pulse current to carry out activation treatment on the proton exchange membrane fuel cell, but the patent has the following defects: and by adopting a current activation mode, the limit current needs to be tested every pulse cycle, so that the activation time is prolonged.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for quickly activating a proton exchange membrane fuel cell stack, which aims at the key position of membrane electrode activation by utilizing different activation means to carry out targeted activation, and adds under-oxygen activation to quickly reduce platinum oxide; the pulse current activation constantly breaks the water balance between the membranes, makes moisture lock on the membrane, through wetting in earlier stage to proton exchange membrane, establishes good ion channel for the activation galvanic pile, and reduce the oxide on catalyst surface, thereby improve the activity of catalyst, promote the utilization ratio of catalyst, and greatly shortened the time of fuel cell galvanic pile activation, reduced hydrogen use amount, practice thrift the cost.
The purpose of the invention can be realized by the following technical scheme:
a method for rapidly activating a proton exchange membrane fuel cell stack comprises the following specific steps:
n1, placing the proton exchange membrane fuel cell on a test platform, connecting a gas pipeline, and checking the air tightness of the galvanic pile;
step N2, setting the temperature of the fuel cell to be 1, introducing humidifying nitrogen into a cathode, introducing humidifying hydrogen into an anode, wherein the humidity of the cathode and the humidity of the anode are respectively 1 and 2, the flow of the cathode is 1, the flow of the anode is 2, and the back pressure of the cathode and the anode is respectively 1 and 2;
step N3, after the temperature of the galvanic pile reaches 1 and maintains the temperature of the galvanic pile for 1 time T1, ending the pre-activation process of the galvanic pile, and setting the temperature of the galvanic pile to be 2;
n4, stopping introducing nitrogen into the cathode after the temperature of the galvanic pile reaches 2, controlling the flow of the cathode and the anode to be in a metering ratio mode after the temperature of the galvanic pile is stabilized, introducing humidified air, wherein the minimum flow of the cathode is 3, the metering ratio is 1, the humidity is 3, the minimum flow of the anode is 4, the metering ratio is 2, the humidity is 4, and the back pressure of the cathode and the anode is respectively 3 pressure and 4 pressure;
step N5, under-oxygen activation: loading the galvanic pile to a voltage 1, stopping introducing air into the cathode, reducing the voltage of the galvanic pile to a voltage 2, introducing air again, disconnecting the load, recovering the voltage to OCV, and repeating the step K1;
and step N6, activating by circulating pulse current:
n6.1, the electric pile is loaded with voltage 3 by OCV,
n6.2, quickly loaded to voltage 4,
n6.3 and then back to voltage 3,
repeating the steps N6.2 and N6.3K2 times, loading the galvanic pile to the voltage 4, stabilizing the running time T2, and obtaining a polarization curve 1 by a linear scanning method, wherein the abscissa of the polarization curve 1 is the current density, and the ordinate is the average voltage;
step N7, repeating the steps N5 and N6 to obtain a polarization curve 2, wherein the abscissa of the polarization curve 2 is current density, the ordinate is average voltage, whether the voltage deviation between the polarization curve 2 and the polarization curve 1 is less than 10mV within the voltage range of 0.55V-0.75V and under the same current is judged, and if yes, the activation of the galvanic pile is judged to be completed; and if the voltage deviation between the polarization curve 2 and the polarization curve 1 is more than or equal to 10mV, repeating the step N7 until the voltage deviation between the new polarization curve and the previous polarization curve is less than 10mV, and finishing the activation of the galvanic pile.
Further, the method comprises a step N0 before the step N1, detecting whether the air tightness of the galvanic pile meets an air tightness index, entering the step N1 if the air tightness index is met, and reassembling the galvanic pile if the air tightness index is not met until the air tightness of the galvanic pile meets the air tightness index.
Further, in step N2, the calculation formula of the flow rate 1 is: 0.00696 active area current density number of single cell meter ratio;
the calculation formula of the flow 2 is as follows: 0.01657 active area current density single cell number metering ratio,
the galvanic pile comprises a plurality of single-chip cells, the effective area is the area of the single-chip cells, the value range of the metering ratio is 1-3, and the current density is the input value of an external device of the galvanic pile.
Further, in step N2, the pressure 1 and the pressure 2 are normal pressures, wherein both the pressures 1 and 2 are gauge pressures.
Further, in step N2, the stack temperature 1 is 60 ℃.
Further, in step N2, the humidity 1= humidity 2= relative humidity value is 100%.
Further, in the step N3, the specific setting manner that the temperature of the stack reaches the temperature 1 is as follows: the cooling liquid is heated to 1 ℃ in advance and maintained at 1 ℃, and the cooling liquid with the first temperature value is introduced into the galvanic pile for temperature rise treatment.
Further, in the step N3, the T1 is 1-5min.
Further, in step N3, the stack temperature 2 is 70 ℃.
Further, in step N4, the calculation formula of the flow 3 is: 0.00696 active area current density number of single cell metric ratio;
the calculation formula of the flow 4 is as follows: 0.01657 active area current density single cell number metering ratio,
the galvanic pile comprises a plurality of single-chip cells, the effective area is the area of the single-chip cells, the value range of the metering ratio is 1-3, and the current density is the input value of an external device of the galvanic pile.
Further, the flow rate 1 is equal to the flow rate 3, and the flow rate 2 is equal to the flow rate 4.
In step N4, the pressure 3 is 100kPa to 150kPa, and the pressure 4 is 100kPa to 150kPa, wherein both pressures 3 and 4 are gauge pressures, and the pressure 4 is 10 kPa to 20kPa higher than the pressure 3.
Further, in step N4, the humidity 3= humidity 4= relative humidity value is 60%.
Further, in step N5, the voltage 1 is 0.8V, and the voltage 2 is 0.3V.
Further, in the step N5, the number of the K1 is 5 to 10.
Further, in step N6, the sweep range OCV of the linear sweep method is-0.5V, the sweep speed is 5mV/s, and OCV is the open circuit voltage.
Further, in the step N6, the T2 is 1-5min.
Further, in the step N6, the voltage 3 is 0.6 to 0.7V, and the voltage 4 is 0.4 to 0.5V.
Further, in the step N6, the number of K2 is 10-20.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, the oxide on the surface of the catalyst is reduced, so that the activity of the catalyst is improved, and the utilization rate of the catalyst is improved;
2. the invention fully wets the proton exchange membrane, constructs a high-efficiency and stable three-phase reaction interface and a good gas-liquid transmission channel in the membrane electrode, and removes impurities in the polymer electrolyte membrane or the electrode to improve the ionic conductivity;
3. compared with the traditional constant current activation method of large current forced discharge, the method adds under-oxygen activation and cyclic pulse activation, quickly reduces oxides and fully wets a proton exchange membrane, improves the activity of the catalyst, establishes a good ion channel, shortens the activation time, and does not need to test limit current by adopting a voltage activation mode.
Drawings
FIG. 1 is a flow chart of the steps of a method for rapid activation of a PEM fuel cell stack according to the present invention;
FIG. 2 is a schematic diagram of an activation cycle of steps N5, N6 according to an embodiment of the present invention;
FIG. 3 is a comparison graph of polarization curves obtained in the examples;
FIG. 4 is a comparison of polarization curves obtained for comparative examples.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
A method for rapidly activating a proton exchange membrane fuel cell stack comprises the following specific steps:
n1, placing the proton exchange membrane fuel cell on a test platform, connecting a gas pipeline, and checking the air tightness of the galvanic pile;
step N2, setting the temperature of the fuel cell to be 1, introducing humidifying nitrogen into a cathode, introducing humidifying hydrogen into an anode, wherein the humidity of the cathode and the humidity of the anode are respectively 1 and 2, the flow of the cathode is 1, the flow of the anode is 2, and the back pressure of the cathode and the anode is respectively 1 and 2;
step N3, when the temperature of the galvanic pile reaches 1 and the temperature of the galvanic pile is maintained for 1 time T1, ending the pre-activation process of the galvanic pile, and setting the temperature of the galvanic pile to be 2;
n4, stopping introducing nitrogen into the cathode after the temperature of the galvanic pile reaches 2, controlling the flow of the cathode and the anode to be in a metering ratio mode after the temperature of the galvanic pile is stabilized, introducing humidified air, wherein the minimum flow of the cathode is 3, the metering ratio is 1, the humidity is 3, the minimum flow of the anode is 4, the metering ratio is 2, the humidity is 4, and the back pressure of the cathode and the anode is respectively 3 pressure and 4 pressure;
step N5, under-oxygen activation: loading the galvanic pile to a voltage 1, stopping introducing air into the cathode, reducing the voltage of the galvanic pile to a voltage 2, introducing air again, disconnecting the load, recovering the voltage to OCV, and repeating the step K1;
and step N6, activating by circulating pulse current:
n6.1, the electric pile is loaded with voltage 3 by OCV,
n6.2, quickly loaded to voltage 4,
n6.3 and then back to voltage 3,
repeating the steps N6.2 and N6.3K2 times, loading the galvanic pile to the voltage 4, stabilizing the operation time T2, and obtaining a polarization curve 1 by a linear scanning method, wherein the abscissa of the polarization curve 1 is the current density, and the ordinate is the average voltage;
step N7, repeating the steps N5 and N6 to obtain a polarization curve 2, wherein the abscissa of the polarization curve 2 is current density, the ordinate is average voltage, whether the voltage deviation between the polarization curve 2 and the polarization curve 1 is smaller than 10mV within the voltage range of 0.55V-0.75V and under the same current is judged, and if yes, activation of the galvanic pile is judged to be completed; and if the voltage deviation between the polarization curve 2 and the polarization curve 1 is more than or equal to 10mV, repeating the step N7 until the voltage deviation between the new polarization curve and the previous polarization curve is less than 10mV, and finishing the activation of the galvanic pile.
Further, the method comprises a step N0 before the step N1, detecting whether the air tightness of the galvanic pile meets an air tightness index, entering the step N1 if the air tightness index is met, and reassembling the galvanic pile if the air tightness index is not met until the air tightness of the galvanic pile meets the air tightness index.
Further, in step N2, the calculation formula of the flow rate 1 is: 0.00696 active area current density number of single cell meter ratio;
the calculation formula of the flow 2 is as follows: 0.01657 active area current density single cell number metering ratio,
the galvanic pile comprises a plurality of single-chip cells, the effective area is the area of the single-chip cells, the value range of the metering ratio is 1-3, and the current density is the input value of an external device of the galvanic pile.
Further, in step N2, the pressure 1 and the pressure 2 are normal pressures, wherein both the pressures 1 and 2 are gauge pressures.
Further, in step N2, the stack temperature 1 is 60 ℃.
Further, in step N2, the humidity 1= humidity 2= relative humidity value of 100%.
Further, in the step N3, the specific setting manner that the temperature of the stack reaches the temperature 1 is as follows: the cooling liquid is heated to 1 ℃ in advance and maintained at 1 ℃, and the cooling liquid with the first temperature value is introduced into the galvanic pile for temperature rise treatment.
Further, in the step N3, the T1 is 1-5min.
Further, in step N3, the stack temperature 2 is 70 ℃.
Further, in step N4, the calculation formula of the flow 3 is: 0.00696 active area current density number of single cell meter ratio;
the calculation formula of the flow 4 is as follows: 0.01657 active area current density single cell number metering ratio,
the galvanic pile comprises a plurality of single-chip cells, the effective area is the area of the single-chip cells, the value range of the metering ratio is 1-3, and the current density is the input value of an external device of the galvanic pile.
Further, the flow rate 1 is equal to the flow rate 3, and the flow rate 2 is equal to the flow rate 4.
In step N4, the pressure 3 is 100kPa to 150kPa, the pressure 4 is 100kPa to 150kPa, wherein, the pressures 3 and 4 are gage pressures, and the pressure 4 is 10 kPa to 20kPa higher than the pressure 3.
Further, in step N4, the humidity 3= humidity 4= relative humidity value is 60%.
Further, in step N5, the voltage 1 is 0.8V, and the voltage 2 is 0.3V.
Further, in the step N5, the number of the K1 is 5 to 10.
Further, in step N6, the scan range OCV of the linear scanning method is 0.5V, the scan speed is 5mV/s, and the OCV is the open circuit voltage.
Further, in the step N6, the T2 is 1-5min.
Further, in the step N6, the voltage 3 is 0.6 to 0.7V, and the voltage 4 is 0.4 to 0.5V.
Further, in the step N6, the number of K2 is 10-20.
The invention is further illustrated with reference to the following figures and examples.
Examples
Referring to fig. 1 to 3, the present embodiment provides a method for rapidly activating a pem fuel cell stack, including the following steps:
the test samples in this implementation were: 1 sheet with an effective area of 25cm 2 And activating the electric pile consisting of the membrane electrode.
N0, detecting whether the air tightness of the galvanic pile meets the air tightness index, entering the step N1 if the air tightness index is met, and reassembling the galvanic pile if the air tightness index is not met until the air tightness of the galvanic pile meets the air tightness index;
n1, placing the proton exchange membrane fuel cell on a test platform, connecting a gas pipeline, and checking the air tightness of the galvanic pile;
and step N2, setting the temperature of the fuel cell to be 60 ℃, introducing humidifying nitrogen into the cathode, introducing humidifying hydrogen into the anode, purging the cathode and the anode by using nitrogen for 20s, wherein the humidity of the cathode and the anode is 100%, the gas pressure of the cathode and the anode is normal pressure, the flow of the cathode is 1, and the purging flow of the cathode nitrogen is 0.5A/cm when the electric pile normally operates, wherein the purging flow of the cathode is 1 2 The following gas flow rates: 0.01657 × 25 × 0.5 × 2.5=0.518L/min, the anode flow is 2, and the anode hydrogen purging flow 2 is 0.5A/cm when the electric pile normally operates 2 The following gas flow rates: 0.00696 × 25 × 0.5 × 1.8=0.157l/min;
step N3, when the temperature of the galvanic pile reaches 60 ℃, maintaining the temperature of the galvanic pile at 60 ℃ for 5min, finishing the pre-activation process of the galvanic pile, and setting the temperature of the galvanic pile at 70 ℃;
n4, stopping introducing nitrogen into the cathode when the temperature of the galvanic pile reaches 70 ℃, controlling the flow of the cathode and the anode to be in a metering ratio mode, introducing humidified air, controlling the minimum flow of the cathode to be 0.518L/min, the metering ratio to be 2.5, the gas pressure to be 90Kpa, the humidity to be 60%, the minimum flow of the anode to be 0.157L/min, the metering ratio to be 1.8, the gas pressure to be 100Kpa and the humidity to be 60%;
step N5, under-oxygen activation: loading the galvanic pile to the voltage of 0.8V, stopping introducing air into the cathode, reducing the voltage of the galvanic pile to 0.3V, introducing air again, disconnecting the load, recovering the voltage to OCV, and repeating the step for 5 times;
and step N6, activating by circulating pulse current:
n6.1, the electric pile is loaded with 0.6V by OCV,
n6.2, rapidly loaded to 0.4V,
n6.3 and then back to 0.6V,
and repeating the steps N6.2 and N6.3 for 20 times, then loading the galvanic pile to 0.4V, stably running for 2min, and obtaining a polarization curve 1 by using a linear scanning method, wherein the scanning range OCV of the linear scanning method is-0.5V, the scanning speed is 5mV/s, and the OCV is open-circuit voltage.
Step N7, repeating the steps N5 and N6 to obtain a polarization curve 2, judging whether the voltage deviation between the polarization curve 2 and the polarization curve 1 is less than 10mV under the voltage of 0.4V and the voltage of 0.6V and under the same current, and if so, judging that the activation of the galvanic pile is finished; and if the voltage deviation between the polarization curve 2 and the polarization curve 1 is more than or equal to 10mV, repeating the step N7 until the voltage deviation between the new polarization curve and the previous polarization curve is less than 10mV, and finishing the activation of the galvanic pile.
As shown in fig. 3, a comparison of polarization curves obtained for this implementation.
As shown in fig. 3, the activation is performed for 6 cycles, where the polarization curve 1 is the polarization curve obtained from the first cycle of activation, and the polarization curves 2 and 3 are the polarization curves obtained from the last two cycles. The first five cycles of the activation process were activated, with a voltage offset value of greater than 10mV relative to the previous cycle, and therefore the sixth activation cycle was performed. The voltage deviation value of the fifth cycle activation and the fourth cycle activation is less than 10mV. And completing the activation of the galvanic pile. This activation took 70min in total.
The embodiment adds under-oxygen activation and cyclic pulse activation, quickly reduces oxides and fully wets a proton exchange membrane, improves the activity of the catalyst, establishes a good ion channel and shortens the activation time.
Comparative example
The comparative example is a conventional activation mode, and is a conventional constant current activation. The comparative example specifically included the following steps:
the test sample of this implementation is: 1 effective area of 25cm 2 And activating the electric pile formed by the membrane electrode.
N0, detecting whether the air tightness of the galvanic pile meets the air tightness index, if so, entering a step N1, and if not, reassembling the galvanic pile until the air tightness of the galvanic pile meets the air tightness index;
n1, placing the proton exchange membrane fuel cell on a test platform, connecting a gas pipeline, and checking the air tightness of the galvanic pile;
and step N2, setting the temperature of the fuel cell to be 60 ℃, introducing humidifying nitrogen into the cathode, introducing humidifying hydrogen into the anode, purging the cathode and the anode by using nitrogen for 20s, wherein the humidity of the cathode and the anode is 100%, the gas pressure of the cathode and the anode is normal pressure, the flow of the cathode is 1, and the purging flow of the cathode nitrogen is 0.5A/cm when the electric pile normally operates, wherein the purging flow of the cathode is 1 2 The following gas flow rates: 0.01657 × 25 × 0.5 × 2.5=0.518L/min, the anode flow is 2, and the anode hydrogen purging flow 2 is 0.5A/cm when the electric pile normally operates 2 The following gas flow rates: 0.00696 × 25.5 × 1.8=0.157l/min;
step N3, when the temperature of the galvanic pile reaches 60 ℃, maintaining the temperature of the galvanic pile at 60 ℃ for 5min, finishing the pre-activation process of the galvanic pile, and setting the temperature of the galvanic pile at 70 ℃;
n4, after the temperature of the galvanic pile reaches 70 ℃, after the galvanic pile is stabilized, stopping introducing nitrogen into the cathode, controlling the flow of the cathode and the anode to be in a metering ratio mode, introducing humidified air, wherein the minimum flow of the cathode is 0.518L/min, the metering ratio is 2.5, the gas pressure is 90Kpa, the humidity is 60%, the minimum flow of the anode is 0.157L/min, the metering ratio is 1.8, the gas pressure is 100Kpa, and the humidity is 60%;
step N5, constant current discharge activation: 0.5V is loaded from OCV, and the loading rate is 0.2A/cm 2 Every 0.2A/cm 2 Staying for 3-5min at a rate of 0.2A/cm 2 And taking the value of the last point to form a polarization curve 1.
Step N6, repeating the step N5 to obtain a polarization curve 2, judging whether the voltage deviation between the polarization curve 2 and the polarization curve 1 is less than 10mV under the same current, and if so, judging that the activation of the galvanic pile is finished; and if the voltage deviation between the polarization curve 2 and the polarization curve 1 is more than or equal to 10mV, repeating the step N6 until the voltage deviation between the new polarization curve and the previous polarization curve is less than 10mV, and finishing the activation of the galvanic pile.
As shown in fig. 4, a comparative plot of the polarization curves obtained for this implementation.
As shown in fig. 4, the activation is performed for 7 cycles, where polarization curve 1 is the polarization curve obtained from one cycle of activation, and polarization curves 2 and 3 are the polarization curves obtained from the last two cycles. The sum voltage deviation value of the seventh cycle activation and the sixth cycle activation is less than 10mV. And completing the activation of the galvanic pile. The total time of this activation is 210min.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make modifications and alterations without departing from the scope of the present invention.
Claims (10)
1. A method for rapidly activating a proton exchange membrane fuel cell stack is characterized by comprising the following specific steps:
n1, placing the proton exchange membrane fuel cell on a test platform, connecting a gas pipeline, and checking the air tightness of the galvanic pile;
step N2, setting the temperature of the fuel cell to be 1, introducing humidifying nitrogen into a cathode, introducing humidifying hydrogen into an anode, wherein the humidity of the cathode and the humidity of the anode are respectively 1 and 2, the flow of the cathode is 1, the flow of the anode is 2, and the back pressure of the cathode and the anode is respectively 1 and 2;
step N3, after the temperature of the galvanic pile reaches 1 and maintains the temperature of the galvanic pile for 1 time T1, ending the pre-activation process of the galvanic pile, and setting the temperature of the galvanic pile to be 2;
n4, stopping introducing nitrogen into the cathode after the temperature of the galvanic pile reaches 2, controlling the flow of the cathode and the anode to be in a metering ratio mode after the temperature of the galvanic pile is stabilized, introducing humidified air, wherein the minimum flow of the cathode is 3, the metering ratio is 1, the humidity is 3, the minimum flow of the anode is 4, the metering ratio is 2, the humidity is 4, and the back pressure of the cathode and the anode is respectively 3 pressure and 4 pressure;
step N5, oxygen deficiency activation: loading the galvanic pile to a voltage 1, stopping introducing air into the cathode, reducing the voltage of the galvanic pile to a voltage 2, introducing air again, disconnecting the load, recovering the voltage to OCV, and repeating the step K1;
and step N6, activating by circulating pulse current:
n6.1, the electric pile is loaded with voltage 3 by OCV,
n6.2, quickly loaded to voltage 4,
n6.3 and then back to voltage 3,
repeating the steps N6.2 and N6.3K2 times, then loading the galvanic pile to the voltage 4, stabilizing the running time T2, and obtaining a polarization curve 1 by using a linear scanning method, wherein the abscissa of the polarization curve 1 is the current density, and the ordinate is the average voltage;
step N7, repeating the steps N5 and N6 to obtain a polarization curve 2, wherein the abscissa of the polarization curve 2 is current density, the ordinate is average voltage, whether the voltage deviation between the polarization curve 2 and the polarization curve 1 is smaller than 10mV within the voltage range of 0.55V-0.75V and under the same current is judged, and if yes, activation of the galvanic pile is judged to be completed; and if the voltage deviation between the polarization curve 2 and the polarization curve 1 is more than or equal to 10mV, repeating the step N7 until the voltage deviation between the new polarization curve and the previous polarization curve is less than 10mV, and finishing the activation of the galvanic pile.
2. The method for rapidly activating the proton exchange membrane fuel cell stack according to claim 1, wherein the step N1 is preceded by a step N0 of detecting whether the air tightness of the stack meets an air tightness index, if the air tightness index is met, the step N1 is carried out, and if the air tightness index is not met, the stack is reassembled until the air tightness of the stack meets the air tightness index.
3. The method of claim 1, wherein in step N2, the flow rate 1 is calculated as: 0.00696 active area current density number of single cell meter ratio;
the calculation formula of the flow 2 is as follows: 0.01657 active area current density single cell number metering ratio,
the galvanic pile comprises a plurality of single-chip cells, the effective area is the area of the single-chip cells, the value range of the metering ratio is 1-3, and the current density is the input value of an external device of the galvanic pile.
4. The method of claim 1, wherein in step N2, the pressure 1 and the pressure 2 are normal pressures, wherein both the pressures 1 and 2 are gauge pressures;
the temperature of the galvanic pile is 1 ℃ and 60 ℃;
the humidity 1= humidity 2= relative humidity value of 100%.
5. The method for rapidly activating a proton exchange membrane fuel cell stack as claimed in claim 1, wherein in step N3, the specific setting manner for the temperature of the stack to reach 1 is as follows: heating the cooling liquid to 1 ℃ in advance, maintaining the temperature at 1 ℃, and introducing the cooling liquid at the first temperature value into the galvanic pile for heating treatment;
the T1 is 1-5min;
the temperature 2 of the galvanic pile was 70 ℃.
6. The method according to claim 1, wherein in step N4, the flow 3 is calculated by the following formula: 0.00696 active area current density number of single cell metric ratio;
the calculation formula of the flow 4 is as follows: 0.01657 active area current density single cell number metering ratio,
the galvanic pile comprises a plurality of single-chip cells, the effective area is the area of the single-chip cells, the value range of the metering ratio is 1-3, and the current density is the input value of an external device of the galvanic pile.
7. The rapid activation method of proton exchange membrane fuel cell stack as claimed in claim 1, wherein in step N4, the pressure 3 is 100kPa to 150kPa, and the pressure 4 is 100kPa to 150kPa, wherein, both the pressures 3 and 4 are gage pressure, and the pressure 4 is 10 kPa to 20kPa higher than the pressure 3;
humidity 3= humidity 4= relative humidity value 60%.
8. The method of claim 1, wherein the flow rate 1 is equal to the flow rate 3, and the flow rate 2 is equal to the flow rate 4.
9. The method as claimed in claim 1, wherein in step N5, the voltage 1 is 0.8V, and the voltage 2 is 0.3V;
the K1 is 5-10 times.
10. The method for rapidly activating a proton exchange membrane fuel cell stack as claimed in claim 1, wherein in step N6, the scan range OCV of the linear scan method is-0.5V, the scan speed is 5mV/s, and OCV is open-circuit voltage;
the T2 is 1-5min;
the voltage 3 is 0.6-0.7V, and the voltage 4 is 0.4-0.5V;
the K2 is 10 to 20 times.
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| CN117790842B (en) * | 2023-12-28 | 2024-05-31 | 洺源科技(大连)有限公司 | Method for activating MEA (Membrane electrode assembly) of hydrogen fuel cell |
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