CN111342077B - Method for storing water-permeable bipolar plate proton exchange membrane fuel cell - Google Patents
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- CN111342077B CN111342077B CN201811457861.7A CN201811457861A CN111342077B CN 111342077 B CN111342077 B CN 111342077B CN 201811457861 A CN201811457861 A CN 201811457861A CN 111342077 B CN111342077 B CN 111342077B
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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
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/0438—Pressure; Ambient pressure; Flow
- H01M8/04432—Pressure differences, e.g. between anode and cathode
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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
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/0438—Pressure; Ambient pressure; Flow
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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
- H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
- H01M8/04746—Pressure; Flow
- H01M8/04753—Pressure; Flow of fuel cell reactants
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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
- H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
- H01M8/04746—Pressure; Flow
- H01M8/04768—Pressure; Flow of the coolant
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- 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
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Abstract
The invention relates to a storage method of a water-permeable bipolar plate proton exchange membrane fuel cell, which is used for carrying out storage treatment after the fuel cell is stopped. The application of the invention to the treatment of the used permeable bipolar plate fuel cell can avoid excessive water remaining in the hydrogen cavity, the oxygen cavity and the Membrane Electrode Assembly (MEA) of the cell for a long time, prevent the MEA from generating performance attenuation due to long-term water immersion and being damaged due to water icing in a low-temperature environment, and is beneficial to the long-term storage and the secondary (low-temperature) starting operation of the fuel cell.
Description
Technical Field
The invention belongs to the field of fuel cells, and particularly relates to a long-term storage method of a permeable bipolar plate proton exchange membrane fuel cell after parking.
Background
A pem fuel cell is a power generation device that converts chemical energy in fuel and oxidant directly into electrical energy with high efficiency through electrocatalytic reaction on a membrane electrode.
It is well known that fuel cells typically require a gas purge after shutdown. The parking purge objective mainly includes two aspects:
on one hand, liquid water in a Membrane Electrode Assembly (MEA) of the battery, a fuel cavity (hydrogen cavity) and an oxidant cavity (oxygen cavity) can be blown out of the battery through purging, so that the performance attenuation of the MEA due to long-term water soaking is prevented; for a fuel cell that is stored and started in a low-temperature environment (<0 ℃), if the water is not purged cleanly, water freezes and expands in volume under low-temperature conditions, and the MEA components may be damaged destructively, so that the performance of the cell after restarting is seriously affected.
On the other hand, the gas purge can discharge the residual fuel and oxidant in the cell out of the cell, and avoid corrosion of the electrocatalyst support due to the higher potential generated by the cathode and anode (US 5013617, US 5045414).
When the battery is stored after the battery is stopped and purged, the battery pipeline is completely closed, and the gas in the pipeline is generally normal pressure.
The above purging process is suitable for the preservation treatment of the traditional polar plate fuel cell, wherein the traditional polar plate refers to a polar plate with three completely separated polar plates, namely a polar plate hydrogen cavity, an oxygen cavity and a coolant cavity (water cavity). In recent years, a water-permeable bipolar plate proton exchange membrane fuel cell has been developed, which (WO 2008/082402a1, CN 101501909a) has functions of water permeation, gas barrier and humidification in addition to functions of fluid distribution, electric conduction, cooling, fuel and oxidant separation and the like of the conventional bipolar plate due to the presence of a water-permeable plate between a hydrogen/oxygen chamber and a water chamber.
The fuel cell adopting the water-permeable bipolar plate is different from the traditional fuel cell in the processes of blowing, preserving and treating after the shutdown:
the common purging method of the inert gas in the hydrogen-oxygen cavity has no excessive limitation, and only needs to ensure that the gas pressure difference in the hydrogen-oxygen cavity is not higher than the maximum pressure difference which can be borne by a proton exchange membrane. For the permeable bipolar plate fuel cell, in order to keep the permeable and impermeable characteristics of the permeable plate, the permeable bipolar plate is convenient to use next time, and the purging pressure of the oxyhydrogen cavity is required to meet the membrane requirement and is required to be not higher than the bubble point of the permeable plate (namely, the minimum pressure difference between the oxyhydrogen cavity and the water cavity when the permeable plate starts to leak air). In addition, after the purging of the common polar plate fuel cell is finished, the hydrogen cavity, the oxygen cavity and the water cavity of the cell are only required to be sealed, but for the permeable bipolar plate fuel cell, water in the water cavity can also return to the hydrogen-oxygen cavity by utilizing the capillary force generated by the porous structure of the permeable plate after the purging is finished when the cell is stopped, so that the MEA is soaked in the water again, and the performance of the cell is further attenuated.
Therefore, there is an urgent need for a preservation method suitable for the water-permeable bipolar plate fuel cell, which can prevent the performance of the water-permeable bipolar plate fuel cell from being attenuated (or the attenuation amplitude is within an acceptable range) during the placing process after the water-permeable bipolar plate fuel cell is stopped, so that the water-permeable bipolar plate fuel cell can be started and operated normally again.
Disclosure of Invention
The present invention is directed to overcoming the above-mentioned drawbacks and deficiencies of the prior art and providing a method for conserving a permeable bipolar plate pem fuel cell for disposal after the fuel cell is shut down. The specific technical scheme is as follows:
the invention provides a method for storing a water-permeable bipolar plate proton exchange membrane fuel cell, which is a method for storing the fuel cell after the fuel cell is stopped, and comprises the following steps:
as water permeable bipolar plates generally exist in two types: the hydrogen cavity and the water cavity, the oxygen cavity and the water cavity are provided with water permeable plates; in the other case, a water permeable plate is arranged between the oxygen cavity and the water cavity, and the hydrogen cavity and the water cavity are separated from each other and are impermeable to water and air. The two permeable bipolar plate fuel cells have slightly different storage methods, which are respectively introduced as follows:
the conditions of the permeable plates exist in the hydrogen cavity, the water cavity, the oxygen cavity and the water cavity: in the process of placing and storing the battery after the battery is stopped, certain pressure gas is introduced into the hydrogen cavity and the oxygen cavity, and certain pressure difference is kept between the hydrogen cavity and the water cavity of the water-permeable bipolar plate and between the oxygen cavity and the water cavity, so that residual water in the hydrogen cavity and the oxygen cavity enters the water cavity under the action of pressure gradient, liquid water in the hydrogen cavity, the oxygen cavity and the MEA of the battery is removed, and a Membrane Electrode Assembly (MEA) is prevented from being soaked by water. The water-permeable bipolar plate has certain pressure difference between the hydrogen cavity and the water cavity and between the oxygen cavity and the water cavity, which means that the gas pressure of the hydrogen cavity and the gas pressure of the oxygen cavity are higher than that of the water cavity.
For the case where there is a permeable plate between the oxygen chamber and the water chamber only: in the process of placing and storing the battery after the battery is stopped, the hydrogen cavity and the oxygen cavity are filled with a certain pressure gas, the pressure gradient of the hydrogen cavity, the oxygen cavity and the water cavity of the water-permeable bipolar plate is reduced, so that residual water in the inner part of the hydrogen cavity enters the oxygen cavity under the action of pressure gradient, and the water in the oxygen cavity also enters the water cavity under the action of pressure gradient, thereby removing liquid water in the hydrogen cavity, the oxygen cavity and the MEA (membrane electrode assembly) of the battery, and avoiding the MEA (membrane electrode assembly) from being soaked by water. The pressure gradient reduction of the hydrogen cavity, the oxygen cavity and the water cavity of the water-permeable bipolar plate refers to the highest gas pressure of the hydrogen cavity and the lowest gas pressure of the water cavity in the hydrogen cavity, the oxygen cavity and the water cavity.
Based on the above technical scheme, it is preferable that the hydrogen chamber and the oxygen chamber need to be filled with inert gas at a certain pressure, and the certain pressure means that the gas pressure in the hydrogen chamber and the oxygen chamber needs to satisfy the following requirements at the same time:
(1) the pressure difference of the gas in the hydrogen cavity and the oxygen cavity is not higher than the maximum pressure difference which can be borne by the proton exchange membrane, so that the membrane is prevented from being damaged due to overlarge pressure difference at two sides;
(2) the pressure difference between the two sides of the permeable plate is not higher than the bubble point, so that the permeable and airtight characteristics of the permeable plate are prevented from being damaged, and the influence on the next normal use of the battery is avoided.
Based on the technical scheme, preferably, when the permeable plates are arranged between the hydrogen cavity and the water cavity and between the oxygen cavity and the water cavity, the pressure difference between the hydrogen cavity and the water cavity and between the oxygen cavity and the water cavity is not lower than 1kPa (the pressure in the invention is relative pressure), and preferably not lower than 10 kPa.
Based on the technical scheme, preferably, when the water permeable plate exists between the oxygen cavity and the water cavity, the pressure difference between any two cavities of the hydrogen cavity, the oxygen cavity and the water cavity is not lower than 1kPa, and preferably not lower than 10 kPa.
Based on the technical scheme, preferably, because pores in a liquid water transmission medium (comprising a proton exchange membrane, a diffusion layer, a water-permeable bipolar plate and the like) in the fuel cell are in a nano-micropore order, and the water transmission needs time, for the preservation method of the water-permeable bipolar plate proton exchange membrane fuel cell disclosed by the invention, the pressure difference between any two cavities of the hydrogen cavity, the oxygen cavity and the water cavity is kept for not less than 1min, preferably not less than 5min, so that the water in the cell can be fully discharged.
Based on the technical scheme, preferably, gas with certain pressure needs to be introduced into the hydrogen cavity and the oxygen cavity, and the gas refers to air, oxygen or inert gas; the inert gas is nitrogen, argon or helium; the gas is preferably an inert gas.
Advantageous effects
The invention has the advantages that: the application of the invention to the treatment of the used permeable bipolar plate fuel cell can avoid excessive water remaining in the cell for a long time, prevent the performance attenuation of the MEA caused by long-term water soaking or water icing in a low-temperature environment, and is beneficial to the long-term storage and restart of the fuel cell.
Drawings
The gas pressure distribution of the hydrogen chamber, the oxygen chamber and the water chamber in the embodiment of FIG. 1 is schematically shown.
Detailed Description
The present invention is described in detail with reference to the following embodiments in order to make the objects, features and effects of the present invention apparent to those skilled in the art.
Example 1
The total number of the permeable bipolar plate proton exchange membrane fuel cells in the embodiment is 120, the maximum pressure difference which can be borne by the MEA is 50kPa, the permeable plate is positioned between the oxygen cavity and the water cavity, the bubble point is 30kPa, and the water and the air are impermeable between the hydrogen cavity and the water cavity. After the fuel cell is used, the fuel cell needs to be stored in an environment with the low temperature of-5 ℃, and the required treatment method is as follows:
firstly, inert gas nitrogen purging is carried out on the hydrogen-oxygen cavity, the gas pressure between the hydrogen cavity and the oxygen cavity is kept at 20kPa in the purging process, and most of water, residual fuel and oxidant in the hydrogen/oxygen cavity are removed.
And after the ordinary purging is finished, continuously introducing nitrogen into the hydrogen cavity and the oxygen cavity, and keeping the pressure of the hydrogen cavity at 20kPa, the pressure of the oxygen cavity at 15kPa and the pressure of the water cavity at 0 (open to the outside), so that the pressure of the hydrogen cavity, the oxygen cavity and the water cavity of the water-permeable bipolar plate is reduced in a gradient manner, as shown in the attached drawing 1. The pressure of the hydrogen cavity, the oxygen cavity and the water cavity is kept for 10min, residual water in the hydrogen cavity penetrates through the MEA to enter the oxygen cavity under the action of pressure difference in the time period, and then enters the water cavity through the water permeable plate, so that the MEA is prevented from being soaked in water, the damage of freezing of water in the low-temperature environment to the membrane, the catalysis layer and the like is avoided, the battery can be stored at low temperature for a long time, and the normal starting operation of the battery next time is facilitated.
Claims (9)
1. A preservation method of a water-permeable bipolar plate proton exchange membrane fuel cell is characterized in that the preservation method is a preservation method of the fuel cell after shutdown, and the method comprises the following steps:
when the permeable plates are arranged between the hydrogen cavity and the water cavity and between the oxygen cavity and the water cavity of the fuel cell: introducing certain pressure gas into the hydrogen cavity and the oxygen cavity, so that certain pressure difference exists between the hydrogen cavity and the water cavity and between the oxygen cavity and the water cavity, and the pressure is maintained for a period of time, so that residual water in the hydrogen cavity and the oxygen cavity enters the water cavity under the action of pressure gradient;
when the fuel cell has the permeable plate between the oxygen cavity and the water cavity: introducing certain pressure gas into the hydrogen cavity and the oxygen cavity to reduce the pressure of the hydrogen cavity, the oxygen cavity and the water cavity in a gradient manner, and keeping the pressure for a period of time to ensure that the residual water in the hydrogen cavity enters the oxygen cavity under the action of pressure gradient, and the water in the oxygen cavity finally enters the water cavity under the action of pressure gradient;
inert gas with certain pressure is required to be introduced into the hydrogen cavity and the oxygen cavity, and the certain pressure means that the gas pressure in the hydrogen cavity and the oxygen cavity simultaneously meets the following requirements:
(1) the pressure difference of the gas in the hydrogen cavity and the oxygen cavity is not higher than the maximum pressure difference which can be borne by the proton exchange membrane;
(2) the gas pressure difference on the two sides of the permeable plate is not higher than the bubble point of the permeable plate.
2. The method for preserving a water-permeable bipolar plate proton exchange membrane fuel cell as claimed in claim 1, wherein when water-permeable plates are respectively arranged in the hydrogen cavity and the water cavity, and the oxygen cavity and the water cavity, the pressure difference between the hydrogen cavity and the water cavity, and between the oxygen cavity and the water cavity is not lower than 1 kPa.
3. The method for preserving a water permeable bipolar plate proton exchange membrane fuel cell as claimed in claim 2, wherein when water permeable plates are respectively arranged in the hydrogen chamber and the water chamber, and the oxygen chamber and the water chamber, the pressure difference between the hydrogen chamber and the water chamber, and between the oxygen chamber and the water chamber is not lower than 10 kPa.
4. The method for preserving a water-permeable bipolar plate proton exchange membrane fuel cell as claimed in claim 1, wherein the pressure difference between any two of the hydrogen chamber, the oxygen chamber and the water chamber is not lower than 1kPa when the water-permeable plate exists only between the oxygen chamber and the water chamber.
5. The method for preserving a water-permeable bipolar plate proton exchange membrane fuel cell as claimed in claim 4, wherein the pressure difference between any two of the hydrogen chamber, the oxygen chamber and the water chamber is not lower than 10kPa when the water-permeable plate exists only between the oxygen chamber and the water chamber.
6. The method for preserving a water-permeable bipolar plate proton exchange membrane fuel cell as claimed in claim 1, wherein the time for maintaining the pressure is not less than 1 min.
7. The method for conserving the water permeable bipolar plate proton exchange membrane fuel cell of claim 6, wherein the time for maintaining the pressure is not less than 5 min.
8. The method of claim 1 wherein the gas is air, oxygen or an inert gas.
9. The method of preserving a water permeable bipolar plate proton exchange membrane fuel cell as claimed in claim 8, wherein the gaseous inert gas; the inert gas is nitrogen, argon or helium.
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| CN201811457861.7A CN111342077B (en) | 2018-11-30 | 2018-11-30 | Method for storing water-permeable bipolar plate proton exchange membrane fuel cell |
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| CN201811457861.7A CN111342077B (en) | 2018-11-30 | 2018-11-30 | Method for storing water-permeable bipolar plate proton exchange membrane fuel cell |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1374324A2 (en) * | 2001-04-05 | 2004-01-02 | Intech Thüringen GmbH | Fuel cell |
| CN101047255A (en) * | 2006-03-28 | 2007-10-03 | 亚太燃料电池科技股份有限公司 | Gas inlet pressure regulating structure of reaction polar plate of fuel cell |
| CN101110482A (en) * | 2006-07-19 | 2008-01-23 | 中国科学院大连化学物理研究所 | Method for improving fuel cell adaptive capacity to environment below zero |
| CN104713689A (en) * | 2013-12-13 | 2015-06-17 | 中国科学院大连化学物理研究所 | Air leakage detecting method for water-pervious bipolar plate in proton exchange membrane fuel cell stack |
| CN105714325A (en) * | 2014-12-01 | 2016-06-29 | 中国科学院大连化学物理研究所 | Static water supply solid polymer electrolyte water electrolysis device with water permeable plate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1261992B1 (en) * | 2000-03-08 | 2011-05-04 | BDF IP Holdings Ltd. | Membrane exchange humidifier |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1374324A2 (en) * | 2001-04-05 | 2004-01-02 | Intech Thüringen GmbH | Fuel cell |
| CN101047255A (en) * | 2006-03-28 | 2007-10-03 | 亚太燃料电池科技股份有限公司 | Gas inlet pressure regulating structure of reaction polar plate of fuel cell |
| CN101110482A (en) * | 2006-07-19 | 2008-01-23 | 中国科学院大连化学物理研究所 | Method for improving fuel cell adaptive capacity to environment below zero |
| CN104713689A (en) * | 2013-12-13 | 2015-06-17 | 中国科学院大连化学物理研究所 | Air leakage detecting method for water-pervious bipolar plate in proton exchange membrane fuel cell stack |
| CN105714325A (en) * | 2014-12-01 | 2016-06-29 | 中国科学院大连化学物理研究所 | Static water supply solid polymer electrolyte water electrolysis device with water permeable plate |
Non-Patent Citations (1)
| Title |
|---|
| 质子交换膜燃料电池梯度扩散层水传输研究;詹志刚等;《华中科技大学学报（自然科学版）》;20070930;第35卷(第9期);全文 * |
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