CN112928309A - Activation method of commercial large-area fuel cell stack - Google Patents
Activation method of commercial large-area fuel cell stack Download PDFInfo
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- CN112928309A CN112928309A CN202110327702.0A CN202110327702A CN112928309A CN 112928309 A CN112928309 A CN 112928309A CN 202110327702 A CN202110327702 A CN 202110327702A CN 112928309 A CN112928309 A CN 112928309A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
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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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- 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
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Abstract
The invention discloses an activation method of a commercialized large-area fuel cell stack, which comprises the following steps: filling the cathode and anode air inlet channels of the galvanic pile with deionized water; the deionized water is emptied and N with a relative humidity of 100% is added2(ii) a Stop feeding N2Then, introducing hydrogen and air, operating at low electric density and low working temperature, and activating the galvanic pile; after the galvanic pile is activated, setting the activation operation condition of the galvanic pile; carrying out continuous variable current forced activation on the fuel cell, carrying current to a preset current value from an open circuit at a constant speed, and carrying current to the stack at a constant speed to recover the open circuit state after the stack operates for a period of time under the preset current value; and repeating the current changing process until the change values of the average voltage of the galvanic pile and the extreme voltage difference of the single body tend to be stable, and finishing the activation. The invention can be operated repeatedly and produced by batch test to make up for the existing commercial large-area qualityThe lack of activation methods for pem fuel cell stacks.
Description
Technical Field
The invention relates to the field of fuel cells, in particular to an activation method of a commercialized large-area fuel cell stack.
Background
The fuel cell stack is assembled by connecting a plurality of single cells in series, adding current collecting plates and end plates at two ends and then using bolts or binding modes. When the fuel cell stack is assembled, it needs to be activated to achieve the optimal state for the vehicle. After the activation treatment, the performance of the galvanic pile gradually rises and reaches the equilibrium, which means the end of the activation process. The activation process and mechanism of the cell stack are very complicated, and the activation process is widely considered at present and comprises the establishment of the following processes: humidifying the proton exchange membrane; establishing a substance (including electrons, protons, gas and water) transmission channel; optimizing the electrode structure; the activity and the utilization rate of the catalyst (mainly cathode Pt) are improved.
The currently used activation methods for fuel cells mainly include the following three processes: 1. natural activation under constant current; 2. constant-current forced activation; 3. the flow is changed to force activation. The current density, the battery temperature and the gas pressure adopted by the constant-current natural activation and the constant-current forced activation are lower, the activation is carried out by long-time constant-current discharge, the activation time is longer, a large amount of hydrogen and an additional humidifying device are consumed by long-time activation, the cost is increased, and the continuous batch production is not facilitated. The existing variable-current forced activation method is mainly an activation method for a single cell with a small area or a short stack with a small number of cell sections, and a method for rapidly activating the stack in batch is lacked for a commercial large-area high-power fuel cell stack.
Disclosure of Invention
The invention aims to provide an activation method of a commercial large-area fuel cell stack, which can be operated repeatedly and produced by batch test, so as to make up for the shortage of the existing commercial large-area proton exchange membrane fuel cell stack activation method.
In order to solve the above technical problems, the present invention provides an activation method of a commercial large-area fuel cell stack, comprising the steps of:
s1: filling the cathode and anode inlet channels of the proton exchange membrane fuel cell stack with deionized water;
s2: the deionized water is emptied and N with a relative humidity of 100% is added2Purging the galvanic pile;
s3: stop feeding N2Then, introducing hydrogen and air, operating at low electric density and low working temperature, and activating the galvanic pile;
s4: after the galvanic pile is activated, setting the activation operation condition of the galvanic pile according to the galvanic pile condition sensitivity experiment;
s5: under the activation condition, the fuel cell is subjected to continuous variable current forced activation, the galvanic pile is pulled to carry current to a preset current value at a constant speed from an open circuit, and under the preset current value, the galvanic pile is operated for a period of time and then is reduced to carry current at a constant speed until the galvanic pile is recovered to an open circuit state;
s6: and repeating the step S5 until the change value of the average voltage of the galvanic pile and the voltage difference of the extreme value of the single body tend to be stable when the load is pulled to the preset current value each time, and finishing the activation.
As a further improvement of the invention, the method also comprises the following steps:
s7: after the activation of the galvanic pile is finished, under the activation operation condition of step S4, continuously and forcibly increasing the current of the galvanic pile at a constant speed until the average voltage of the galvanic pile is less than or equal to 0.6V or the extreme voltage difference of the monomer is greater than or equal to 40mV, adjusting the operation condition of the galvanic pile to the peak power test condition, continuously and forcibly increasing the current at a constant speed until the average voltage of the galvanic pile is less than or equal to 0.6V or the extreme voltage difference of the monomer is greater than or equal to 40mV, and then reducing the current at a constant speed to an open circuit state;
s8: and repeating the operation steps under the condition of the peak power test in the step S7 until the current value of the galvanic pile can not be continuously pulled up when the average voltage of the galvanic pile is less than or equal to 0.6V or the voltage difference of the extreme value of the single body is more than or equal to 40mV, so as to obtain the maximum peak power of the galvanic pile.
As a further improvement of the present invention, the preset current value is smaller than a final current value at which the pull-up cannot be continued in the step S8.
As a further improvement of the invention, the proton exchange membrane fuel cell stack is capable of performing a polarization curve test under peak power test conditions.
As a further improvement of the present invention, the temperature of the deionized water in the step S1 is 40 ℃.
As a further improvement of the invention, the metering ratio of the introduced hydrogen and the introduced air in the step S3 is 2:3, and the low electric density is less than 0.5A/cm2The low working temperature is lower than 60 ℃, and the operation is carried out for at least 3min to activate the galvanic pile.
As a further improvement of the present invention, the activation operation conditions in the step S4 include gas pressure, relative humidity, inlet coolant temperature and H of the anode and the cathode2And air usage.
As a further improvement of the invention, the active area is 260cm2The 168-piece proton exchange membrane fuel cell stack of (1), wherein the activation operating conditions are that the gas pressure of the anode and the gas pressure of the cathode are respectively 90kpa and 80kpa, the relative humidity RH 70%, the inlet coolant temperature is 58 ℃ and H2And the air usage was 1.7: 2.7.
As a further improvement of the present invention, the preset current value in step S5 is 340A, and after the stack is operated for 3min under 340A, the current is reduced at a constant rate until the stack returns to the open circuit state.
As a further improvement of the invention, the peak power test conditions are anode and cathode gas pressures of 110kpa and 100kpa, respectively, relative humidity RH 60%, inlet coolant temperature 63 deg.C and H2And the air usage was 1.5: 2.4.
The invention has the beneficial effects that: the invention achieves the preheating effect by wetting the proton exchange membrane and activating the galvanic pile, carries out the current-converting forced activation by the optimized running condition of the galvanic pile, carries out different and targeted regulation and control on the discharge current, can carry out repeated operation on the galvanic pile, has consistent activation effect, can carry out commercial batch test, leads the galvanic pile to be completely activated by the stable judgment of the change value of the average voltage of the galvanic pile and the extreme voltage difference of the monomer, accurately judges the activation standard, avoids the galvanic pile from not reaching the complete activation effect, and effectively ensures the service performance of the galvanic pile.
Drawings
FIG. 1 is a graph showing the number of activation cycles and the change of the average voltage value during the activation process according to the second and third embodiments of the present invention;
FIG. 2 is a schematic representation of the polarization curves of example two and example three of the present invention before and after activation;
FIG. 3 is a schematic illustration of the polarization curves after activation and peak power measurement for example three of the present invention.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
Example one
The embodiment of the invention provides an activation method of a commercial large-area fuel cell stack, which comprises the following steps:
s1: filling the cathode and anode inlet channels of the proton exchange membrane fuel cell stack with deionized water;
s2: the deionized water is emptied and N with a relative humidity of 100% is added2Purging the galvanic pile;
s3: stop feeding N2Then, introducing hydrogen and air, operating at low electric density and low working temperature, and activating the galvanic pile;
s4: after the galvanic pile is activated, setting the activation operation condition of the galvanic pile according to the galvanic pile condition sensitivity experiment;
s5: under the activation condition, the fuel cell is subjected to continuous variable current forced activation, the galvanic pile is pulled to carry current to a preset current value at a constant speed from an open circuit, and under the preset current value, the galvanic pile is operated for a period of time and then is reduced to carry current at a constant speed until the galvanic pile is recovered to an open circuit state;
s6: and repeating the step S5 until the change value of the average voltage of the galvanic pile and the voltage difference of the extreme value of the single body tend to be stable when the load is pulled to the preset current value each time, and finishing the activation.
Specifically, the temperature of the deionized water in the step S1 is 40 ℃; in the step S3, the metering ratio of the introduced hydrogen to the introduced air is 2:3, and the low electric density is less than 0.5A/cm2The low working temperature is lower than 60 ℃, and the operation is carried out for at least 3min to activate the galvanic pile; the activation operating conditions in step S4 include anode and cathode gas pressures, relative humidity, inlet coolant temperature, and H2 and air usage ratios. According to the method for activating the fuel cell stack, the proton exchange membrane of the fuel cell stack is wetted, a preliminary substance transmission channel is established through activation of the stack, and meanwhile, the temperature of the stack reaches the normal working temperature and the inside of the stack is basically wetted, so that the preheating effect is achieved; secondly, current transformation forced activation is carried out through optimized operation conditions of the galvanic pile, different and targeted regulation and control are carried out on discharge current, after discharge circulation for many times, the performance of the galvanic pile is not increased and basically reaches stability, the galvanic pile is completely activated, the activation standard is accurately judged, and the galvanic pile is prevented from not reaching the complete activation effect.
Example two
The embodiment of the invention provides an activation method of a commercial large-area fuel cell stack, which comprises the following steps:
1) the active area is 260cm2The air inlet channels of the cathodes and the anodes of the 168 proton exchange membrane fuel cell stacks are filled with deionized water at the temperature of 40 ℃;
2) emptying cathode and anode deionized water, and introducing atmospheric N with the relative humidity of 100%2Purging;
3) stopping feeding N to cathode and anode of pile2Introducing hydrogen and air in a metering ratio of 2:3 at 0.2A/cm2Operating at 50 deg.C for 3min under electric density to activate the galvanic pile;
4) after activation, the operation conditions of the galvanic pile are set (the anode/cathode pressure is 90kpa/80kpa, the humidity RH is 70%, and the inlet is cold)Coolant temperature 58 deg.C, gas H2The metering ratio of/Air is 1.7:2.7), then the fuel cell stack is subjected to continuous variable current forced activation, namely the stack is subjected to load current pulling from an open circuit to a preset current value 340A at a constant speed, and after the stack runs for 3min under 340A, the load current is reduced to the stack at a constant speed to restore the open circuit state;
5) repeating the activation step 4), recording the average voltage V1 of the cell stack and the maximum-minimum voltage difference Δ V (extreme voltage difference) of the cell when each time the load is pulled to the setting 340A, and when the two change values tend to be stable, the activation is completed, so as to obtain the activation process curve of the example 2 in fig. 1.
After the activation of the electric pile is finished, setting the operation conditions of the electric pile (the anode/cathode pressure is 110kpa/100kpa, the humidity RH is 60%, the temperature of an inlet coolant is 63 ℃, and using gas H2Air metering ratio 1.5:2.4), after stable operation, polarization curve testing is carried out, and the polarization curve after activation of example 2 in fig. 2 is obtained.
From fig. 2, it can be seen that, after the stack is activated, the performance of the activated stack is obviously improved by comparing with that before the activation.
EXAMPLE III
The embodiment of the invention provides an activation method of a commercial large-area fuel cell stack, which comprises the following steps:
1) the active area is 260cm2The air inlet channels of the cathodes and the anodes of the 168 proton exchange membrane fuel cell stacks are filled with deionized water at the temperature of 40 ℃;
2) emptying cathode and anode deionized water, and introducing atmospheric N with the relative humidity of 100%2Purging;
3) stopping feeding N to cathode and anode of pile2Introducing hydrogen and air in a metering ratio of 2:3 at 0.2A/cm2Operating at 50 deg.C for 3min under electric density to activate the galvanic pile;
4) after activation, the operation condition a1 of the stack is set (anode/cathode pressure 90kpa/80kpa, humidity RH 70%, inlet coolant temperature 58 ℃, using gas H2The Air metering ratio is 1.7:2.7), and then the fuel cell stack is subjected to continuous variable current forced activation, namely the stack is subjected to constant speed from an open circuitPulling the load current to a preset current value 340A, and reducing the load current at a constant speed until the galvanic pile recovers an open circuit state after the galvanic pile runs for 3min under 340A;
5) repeating the activation step 4), recording the average voltage V1 of the galvanic pile and the maximum-minimum voltage difference delta V of the monomer when each time the load is pulled to the set value 340A, and completing the activation when the two change values tend to be stable, thereby obtaining the activation process curve of the embodiment 3 in the figure 1;
after the activation of the stack is completed, the operation condition A2 of the stack is set (the anode/cathode pressure is 110kpa/100kpa, the humidity RH is 60%, the temperature of the inlet coolant is 63 ℃, and the gas H is used2The Air metering ratio is 1.5:2.4), after stable operation, carrying out polarization curve test to obtain a polarization curve after activation in the embodiment 3 in the figures 2 and 3, which can be obtained from the figure 2, and the performance of the activated galvanic pile is obviously improved by comparing the performance of the galvanic pile after activation with that before activation;
6) after the activation of the galvanic pile is finished, under a test condition A1, the galvanic pile carries out continuous voltage-changing forced current rise at a constant speed until the average voltage of the galvanic pile is less than or equal to 0.6V or the maximum-minimum voltage difference of the monomer is more than or equal to 40mV, the running condition of the galvanic pile is adjusted to a test condition A2, continuous voltage-changing forced current rise is carried out at a constant speed until the average voltage of the galvanic pile is less than or equal to 0.6V or the maximum-minimum voltage difference of the monomer is more than or equal to 40mV, and then the current is carried down to an open circuit state at a constant speed;
7) repeating the step 6) of testing the peak power until the current value of the galvanic pile can not be continuously pulled up when the average voltage of the galvanic pile is less than or equal to 0.6V or the maximum-minimum voltage difference of the monomer is more than or equal to 40 mV; the stack was tested for polarization curve under test condition a2 to obtain the polarization curve after the peak value of example 3 in fig. 3.
As can be seen from fig. 3, after the activation of the stack is completed, the performance of each cell is considered under the precondition that the operation conditions are not changed, and the performance of the stack can be further improved by the control method, so that the maximum peak power can be obtained optimally.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. A method of activating a commercial large area fuel cell stack, comprising: the method comprises the following steps:
s1: filling the cathode and anode inlet channels of the proton exchange membrane fuel cell stack with deionized water;
s2: the deionized water is emptied and N with a relative humidity of 100% is added2Purging the galvanic pile;
s3: stop feeding N2Then, introducing hydrogen and air, operating at low electric density and low working temperature, and activating the galvanic pile;
s4: after the galvanic pile is activated, setting the activation operation condition of the galvanic pile according to the galvanic pile condition sensitivity experiment;
s5: under the activation condition, the fuel cell is subjected to continuous variable current forced activation, the galvanic pile is pulled to carry current to a preset current value at a constant speed from an open circuit, and under the preset current value, the galvanic pile is operated for a period of time and then is reduced to carry current at a constant speed until the galvanic pile is recovered to an open circuit state;
s6: and repeating the step S5 until the change value of the average voltage of the galvanic pile and the voltage difference of the extreme value of the single body tend to be stable when the load is pulled to the preset current value each time, and finishing the activation.
2. A method of activating a commercial large area fuel cell stack according to claim 1, wherein: further comprising the steps of:
s7: after the activation of the galvanic pile is finished, under the activation operation condition of step S4, continuously and forcibly increasing the current of the galvanic pile at a constant speed until the average voltage of the galvanic pile is less than or equal to 0.6V or the extreme voltage difference of the monomer is greater than or equal to 40mV, adjusting the operation condition of the galvanic pile to the peak power test condition, continuously and forcibly increasing the current at a constant speed until the average voltage of the galvanic pile is less than or equal to 0.6V or the extreme voltage difference of the monomer is greater than or equal to 40mV, and then reducing the current at a constant speed to an open circuit state;
s8: and repeating the operation steps under the condition of the peak power test in the step S7 until the current value of the galvanic pile can not be continuously pulled up when the average voltage of the galvanic pile is less than or equal to 0.6V or the voltage difference of the extreme value of the single body is more than or equal to 40mV, so as to obtain the maximum peak power of the galvanic pile.
3. A method of activating a commercial large area fuel cell stack according to claim 2, wherein: the preset current value is smaller than the final current value at which the pull-up cannot be continued in step S8.
4. A method of activating a commercial large area fuel cell stack according to claim 2, wherein: the proton exchange membrane fuel cell stack can perform a polarization curve test under a peak power test condition.
5. A method of activating a commercial large area fuel cell stack according to claim 1, wherein: the temperature of the deionized water in the step S1 is 40 ℃.
6. A method of activating a commercial large area fuel cell stack according to claim 1, wherein: the metering ratio of the introduced hydrogen to the air in the step S3 is 2:3, and the low electric density is less than 0.5A/cm2The low working temperature is lower than 60 ℃, and the operation is carried out for at least 3min to activate the galvanic pile.
7. A method of activating a commercial large area fuel cell stack according to claim 1, wherein: the activation operation conditions in the step S4 include gas pressure, relative humidity, inlet coolant temperature, and H of the anode and the cathode2And air usage.
8. The method of any of claims 1-7 for activating a commercial large area fuel cell stackThe method comprises the following steps: for an active area of 260cm2The 168-piece proton exchange membrane fuel cell stack of (1), wherein the activation operating conditions are that the gas pressure of the anode and the gas pressure of the cathode are respectively 90kpa and 80kpa, the relative humidity RH 70%, the inlet coolant temperature is 58 ℃ and H2And the air usage was 1.7: 2.7.
9. A method of activating a commercial large area fuel cell stack according to claim 8, wherein: the preset current value in step S5 is 340A, and after the stack operates for 3min under 340A, the current is then reduced at a constant rate until the stack returns to the open circuit state.
10. A method of activating a commercial large area fuel cell stack according to claim 8, wherein: the peak power test conditions in the step S7 were that the gas pressures of the anode and cathode were 110kpa and 100kpa, respectively, the relative humidity RH 60%, the inlet coolant temperature 63 ℃ and H2And the air usage was 1.5: 2.4.
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| CN114447380A (en) * | 2022-01-18 | 2022-05-06 | 同济大学 | Method for recovering performance of proton exchange membrane fuel cell stack |
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| CN113258102A (en) * | 2021-06-17 | 2021-08-13 | 潍柴动力股份有限公司 | Cell stack activation method and device and storage medium |
| CN113258102B (en) * | 2021-06-17 | 2021-12-21 | 潍柴动力股份有限公司 | Cell stack activation method and device and storage medium |
| CN114284529A (en) * | 2021-12-27 | 2022-04-05 | 深圳市贝特瑞新能源技术研究院有限公司 | Battery activation method and battery activation device |
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| CN114361530A (en) * | 2021-12-28 | 2022-04-15 | 新源动力股份有限公司 | Proton exchange membrane fuel cell stack batch pre-activation method and device |
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| CN114447380A (en) * | 2022-01-18 | 2022-05-06 | 同济大学 | Method for recovering performance of proton exchange membrane fuel cell stack |
| CN114447380B (en) * | 2022-01-18 | 2024-04-26 | 同济大学 | Method for recovering performance of proton exchange membrane fuel cell stack |
| CN114597450A (en) * | 2022-03-09 | 2022-06-07 | 大同氢雄云鼎氢能科技有限公司 | Rapid activation method of fuel cell system |
| CN115064732A (en) * | 2022-07-25 | 2022-09-16 | 中汽创智科技有限公司 | Activation method of proton exchange membrane fuel cell |
| CN115064732B (en) * | 2022-07-25 | 2024-02-23 | 中汽创智科技有限公司 | Activation method of proton exchange membrane fuel cell |
| CN115548382A (en) * | 2022-12-02 | 2022-12-30 | 山东国创燃料电池技术创新中心有限公司 | Activation control method and device for fuel cell stack, fuel cell test bench and medium |
| CN116505025A (en) * | 2023-06-25 | 2023-07-28 | 上海重塑能源科技有限公司 | Method for recovering performance of fuel cell |
| CN116505025B (en) * | 2023-06-25 | 2023-09-01 | 上海重塑能源科技有限公司 | Method for recovering performance of fuel cell |
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