CN110416556A - A kind of method of fuel cell pile activation - Google Patents
A kind of method of fuel cell pile activation Download PDFInfo
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- CN110416556A CN110416556A CN201910602707.2A CN201910602707A CN110416556A CN 110416556 A CN110416556 A CN 110416556A CN 201910602707 A CN201910602707 A CN 201910602707A CN 110416556 A CN110416556 A CN 110416556A
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
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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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- 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 present invention relates to a kind of methods of fuel cell pile activation.Described method includes following steps: (1) carrying out once prewet activation and secondary activation of prewetting to fuel cell the two poles of the earth, then load the first current density to membrane electrode and activate voltage V0；Described once prewet between activation and secondary activation of prewetting further includes generating the process of water in two side reaction of electrode；(2) fuel cell that step (1) obtains is activated under the second current density, is then adjusted single battery voltage to V with third current density1, the third current density < the second current density；(3) fuel cell that step (2) obtains is run under the 4th current density, tests variation △ V of the single battery voltage in time T.Activation process of the present invention is simple, and activation time can control within 2h, meets the needs of mass production, and the fuel cell that activation obtains has good chemical property.
Description
Technical field
The invention belongs to fuel cell fields, and in particular to a kind of method of fuel cell pile activation.
Background technique
Fuel cell is a kind of directly to convert fuel by the electrocatalytic reaction on electrode with the chemical energy in oxidant
For the power generator of electric energy.Fuel cell is not limited by Carnot cycle, efficiently can convert electric energy for chemical energy.Proton
Exchange film fuel battery due to cold-starting, structure is simple, easy to operate the features such as, be most be hopeful be applied to middle length away from
Power resources from electric car.
Optimum performance is rapidly achieved when to enable Proton Exchange Membrane Fuel Cells to work, general fuel cell pile is completed
After assembling, need in advance under prescribed conditions to be activated the electrode in fuel cell pile.Proton exchange membrane combustion
Expect that battery stack activation process and mechanism are extremely complex, the electrode of pile includes the progress of following six kinds of processes simultaneously: proton is handed over
Change the humidification of film, the establishment process of electron propagation ducts, the establishment process of proton transmitting channel, gas delivery passage builds
Vertical process, the establishment process of water transmission channel, the optimization process of electrode structure.
So far, the activation for completing Experimental research on proton exchange membrane fuel cells for vehicles pile takes a long time, and generally 12
~48 hours.Common fuel cell pile activation method mainly has following three kinds of technique: 1, constant current activates naturally；2, constant current is strong
System activation；3, forced activation at varied current.Current density, battery temperature used by constant current at present activates naturally and force constant current to activate
Lower with gas pressure, activation time used is also longer, and activation time is up to 24~48 hours.Even if improved unsteady flow is strong
System activation can foreshorten to the activation time of pile 5~12 hours, but current pile activation time is not able to satisfy pile batch still
Quantify the demand of production.
CN105895938B discloses a kind of activation method of proton exchange film fuel cell electric piling, step are as follows: will just fill
The battery pile of completion is mounted on activation platform, detects air-tightness；N is passed through in the cathode and anode of battery pile2, purging；Setting
Operating temperature；Cathode is passed through the air of the humidification of RH 80%, and anode is passed through the H not being humidified2, often arrange, gas pressure be 60~
100KPa；Using load to battery pile loading current, air and H2Stoichiometric ratio be 3.5 and 1.5 respectively；By air and H
Stoichiometric ratio be set to 3.0 and 1.5, the continuous service 30min under maximum current；0A quickly is lowered the current to, is broken
Open circuit is passed through the cooling battery pile of cooling water, battery pile is cooled to room temperature, then carries out to the battery pile just filled secondary tight
Gu the decrement of battery pile is made to reach the technical indicator of setting.The activation method cannot sufficiently complete activation process, and test
Card pile is no to be completed to activate the temperature switching needed to carry out between high temperature-room temperature, and the stack temperature adjusting in hundreds of section lists pond is compared
Slowly, once performance it is not up to standard needs reactivate, adjustment temperature needs take considerable time, pile in actual use
Performance data meeting sustainable growth, or even the scope of design beyond pile corollary system, bring tired to the mating matched design of system
It disturbs.
CN108232243A discloses a kind of activation method of proton exchange fuel cell, is included in pem fuel
Cell cathode is passed through humidification nitrogen, and anode is passed through humidified hydrogen, checks Proton Exchange Membrane Fuel Cells air-tightness；Battery work is set
Make temperature；After reaching setting temperature, persistently cathode nitrogen and anode hydrogen gas is kept to be passed through 2~3h；Cathode is passed through gas conversion
For the oxygen and/or air of humidification, polarization performance test and/or cyclic voltammetry are carried out to the Proton Exchange Membrane Fuel Cells
Cathode is passed through gas again and is converted to humidification nitrogen, and keeps 10~20min by test 5~10 times；Repeat step 4 10~20
It is secondary, until the Proton Exchange Membrane Fuel Cells polarization performance keeps stablizing.The activation process time is longer, is unable to satisfy batch
The demand that metaplasia produces.
Therefore, a kind of method that this field needs new fuel cell pile activation, sufficiently completes the activation process of activation
Time can control within 2h, meet the needs of mass production, and the fuel cell that activation obtains has good electrification
Learn performance.
Summary of the invention
The purpose of the present invention is to provide a kind of methods of fuel cell pile activation, do not need to be related in activation process
To the switching of temperature, the time for sufficiently completing activation be can control within 2h, meet the needs of mass production, and activate
The fuel cell arrived has good chemical property.
To achieve this purpose, the present invention adopts the following technical scheme:
One of the objects of the present invention is to provide a kind of methods of fuel cell pile activation, and the method includes walking as follows
It is rapid:
(1) once prewet activation and secondary activation of prewetting are carried out to fuel cell the two poles of the earth, then loads the first current density
Voltage V is activated to membrane electrode0；
Described once prewet between activation and secondary activation of prewetting further includes generating the process of water in two side reaction of electrode；
(2) fuel cell that step (1) obtains is activated under the second current density, it then will be single with third current density
Economize on electricity cell voltage is adjusted to V1, the third current density < the second current density；
(3) fuel cell that step (2) obtains is run under the 4th current density, tests single battery voltage in the time
Variation △ V in T.
Once prewet activation and the secondary activation process of prewetting that the present invention passes through pile first form electrode surface quickly
Short time high potential, and then the unstable catalyst and oxidizing electrode surface impurity of electrode surface are eliminated, realize the fast of membrane electrode
Speed activation；Then pass through the humidification activation process of time-dependent current, run under high current density, the water that reaction can be made to generate is humidified rapidly
Membrane electrode realizes the quick humidification of proton exchange membrane, Catalytic Layer resin；By controlling pile reporting to the leadship after accomplishing a task in high and low current density
Operation can make electrode quickly form stable gas, electron propagation ducts, variation △ V of the present invention by test in time T
Judge whether pile is completed to activate, realizes the acceleration activation of fuel cell pile.
Of the present invention once prewet generates water in two side reaction of electrode between activation and secondary activation of prewetting, can be in short-term
Interior heating and wet catalysis layer surface and inside, shorten activation time to the full extent.Activation process of the present invention is simple, activation
Time can control within 2h, minimum up to 1.5h, meet the needs of mass production, and the fuel cell tool that activation obtains
There is good chemical property.
It preferably, further include that pretreated process is carried out to fuel cell before step (1).
Preferably, the preprocessing process includes: to supply fuel to the fuel electrode of the fuel cell, and air electrode supplies
Air is answered, and adjusts the open-circuit voltage V of single battery4For 0.95~1.2V, continue 2~8min, the V4For 0.95~1.2V,
Such as 0.98V, 1V, 1.02V, 1.05V, 1.08V, 1.1V, 1.12V, 1.15V, 1.16V or 1.18V etc.；It is 2~8min described
Such as 3min, 4min, 5min, 6min or 7min.
Preferably, step (1) process for once prewetting activation includes: to be passed through humidified nitrogen to fuel cell the two poles of the earth,
Nitrogen purges pile, until single battery voltage V2≤ 0.5V, for example, 0.28V, 0.3V, 0.32V, 0.35V, 0.38V, 0.40V,
0.42V, 0.45V, 0.48V or 0.49V etc..
Preferably, the V2For 0.3~0.5V, preferably 0.4~0.5V, for example, 0.3V, 0.32V, 0.35V, 0.38V,
0.40V, 0.42V, 0.45V, 0.48V or 0.49V etc..
In the present invention, if V2Excessive, then the fuel of pile fuel electrode side is retained excessive, can be damaged in second step activation
Bad electrode；If V2Too small, pile fuel electrode side cannot retain enough fuel and carry out next step activation act.
Preferably, it is described once prewet activation time be 8~15min, such as 9min, 10min, 11min, 12min,
13min or 14min etc..
Preferably, step (1) process for generating water in two side reaction of electrode includes: after stopping primary activation of prewetting
The nitrogen supply (NS) of two lateral electrodes is passed through air to fuel electrode side, and air electrode side is passed through hydrogen, continues 8~15min.It is described
Time such as 9min, 10min, 11min, 12min, 13min or 14min etc..
The present invention is passed through air after stopping logical fuel, to fuel electrode side, and air electrode side is passed through hydrogen, hydrogen-oxygen mixing
The water that gas is generated in two side reaction of electrode can be contracted to the full extent with heating up in the short time and moistening catalysis layer surface and inside
Short activation time.
Preferably, the fuel includes hydrogen.
Preferably, the process of step (1) the secondary activation of prewetting includes: to be passed through humidified nitrogen to fuel cell the two poles of the earth,
Nitrogen purges pile, until single battery voltage V3≤ 0.5V, for example, 0.28V, 0.3V, 0.32V, 0.35V, 0.38V, 0.40V,
0.42V, 0.45V, 0.48V or 0.49V etc..
Preferably, the V3For 0.3~0.5V, preferably 0.4~0.5V, for example, 0.32V, 0.35V, 0.38V, 0.40V,
0.42V, 0.45V, 0.48V or 0.49V etc..
In the present invention, the V3Too small, then the running current that will lead to pile is excessive, produces to the electrode performance after activation
Raw adverse effect；If V3Excessive, then the running current that will lead to pile is too small, is not enough to the performance of active electrode.
Preferably, described two prewet activation time be 8~15min, such as 9min, 10min, 11min, 12min,
13min or 14min etc..
It preferably, further include stopping two before loading the first current density after step (1) the secondary activation of prewetting
The nitrogen supply (NS) of two lateral electrodes, is then passed through air to air electrode side, fuel electrode side is passed through fuel after secondary activation of prewetting
Process.
Preferably, step (1) first current density >=1A/cm2, preferably 1~1.5A/cm2, such as 1.1A/cm2、
1.2A/cm2、1.4A/cm2、1.5A/cm2、1.6A/cm2、1.8A/cm2、2A/cm2、2.1A/cm2、2.2A/cm2、2.5A/cm2、
2.8A/cm2Or 3A/cm2Deng.
Preferably, step (1) membrane electrode activates voltage V0For the voltage of single battery, preferably 0.6~0.65V,
Such as 0.61V, 0.62V, 0.63V or 0.64V etc..
V of the present invention0For 0.6~0.65V, if V0Less than 0.6V, then the running current that will lead to pile is excessive, to work
Electrode performance after change has an adverse effect；If V0Greater than 0.65V, then the running current that will lead to pile is too small, is not enough to swash
The performance of electrode living.
Preferably, step (1) V0Retention time >=20min, preferably 25~35min, such as 26min,
28min, 30min, 32min, 34min, 35min, 38min, 40min, 42min or 45min etc..
Preferably, step (2) second current density is 1~1.5A/cm2, preferably 1.1~1.3A/cm2, such as
1.1A/cm2、1.2A/cm2、1.3A/cm2Or 1.4A/cm2Deng.
Second current density of the present invention is 1~1.5A/cm2, second current density is less than 1A/cm2When, then it is electric
The running current of heap is too small, is not enough to the performance of active electrode；Second current density is greater than 1.5A/cm2When, then it will lead to
The running current of pile is excessive, has an adverse effect to the electrode performance after activation.
Preferably, the time activated under second current density be 8~15min, such as 9min, 10min, 11min,
12min, 13min or 14min etc..
The time activated under second current density of the present invention is 8~15min, and activation time is too small, then the work of pile
The change time is excessively short and small, is not enough to the performance of active electrode；Activated under second current density when it is excessive, then will lead to pile
Activation time it is too long, waste time, influence activation efficiency.
Preferably, under second current density activate after, further include stop two lateral electrode of fuel cell fuel and
The process of air supply.
Preferably, the third current density is 0.05~0.15A/cm2, preferably 0.08~0.12A/cm2, such as
0.06A/cm2、0.07A/cm2、0.08A/cm2、0.09A/cm2、0.1A/cm2、0.11A/cm2、0.12A/cm2、0.13A/cm2Or
0.14A/cm2Deng.
Preferably, the V1>=0.7V, preferably 0.7~0.9V, further preferably 0.75~0.85V, such as
0.72V, 0.75V, 0.78V, 0.8V, 0.82V, 0.85V, 0.88V, 0.9V, 0.92V or 0.95V etc..
If V in the present invention1Too small, then the running current that will lead to pile is excessive, generates not to the electrode performance after activation
Benefit influences；If V1Excessive, then the running current that will lead to pile is too small, is not enough to the performance of active electrode.
Preferably, the V1The voltage lower retention time be 8~15min, such as 9min, 10min, 11min, 12min,
13min or 14min etc..
It preferably, further include to air electrode side before step (3) described fuel cell is run under the 4th current density
It is passed through air, fuel electrode side is passed through the process of fuel.
Preferably, the 4th current density is 0.1~1.2A/cm2, such as 0.2A/cm2、0.3A/cm2、0.4A/cm2、
0.5A/cm2、0.6A/cm2、0.7A/cm2、0.8A/cm2、0.9A/cm2、1A/cm2Or 1.1A/cm2Deng.
Preferably, the time T is 15~20min, such as 16min, 17min, 18min or 19min etc..
Preferably, the △ V≤10mV, complete fuel cell pile activation, such as 1mV, 2mV, 3mV, 4mV, 5mV,
6mV, 7mV, 8mV or 9mV etc..
Preferably, the △ V > 10mV repeats step (2) and step (3), until the △ V≤10mV；The △
V > 10mV, such as 11mV, 12mV, 13mV, 14mV, 15mV, 16mV, 17mV, 18mV or 19mV etc.；△ V≤the 10mV is for example
1mV, 2mV, 3mV, 4mV, 5mV, 6mV, 7mV, 8mV or 9mV etc..
The present invention controls △ V in 15~20min control in 10mV, can quickly judge whether pile reaches stable state.
Preferably, the total time of the fuel cell pile activation process be 1.5~2.5h, such as 1.6h, 1.7h,
1.8h, 1.9h, 2h, 2.1h, 2.2h, 2.3h or 2.4h etc..
Preferably, the temperature of the fuel cell pile activation process is 55~65 DEG C, such as 56 DEG C, 57 DEG C, 58 DEG C, 59
DEG C, 60 DEG C, 61 DEG C, 62 DEG C, 63 DEG C or 64 DEG C etc..
Preferably, during fuel cell pile activation, the humidified nitrogen relative humidity being passed through is 70%~
100%, such as 75%, 80%, 82%, 85%, 88%, 90%, 92%, 95% or 98% etc..
Preferably, during the fuel cell pile activation, the relative air humidity being passed through is 70%~100%,
Such as 75%, 80%, 82%, 85%, 88%, 90%, 92%, 95% or 98% etc..
Preferably, during the fuel cell pile activation, the fuel relative humidity being passed through is 70%~100%,
Such as 75%, 80%, 82%, 85%, 88%, 90%, 92%, 95% or 98% etc..
As optimal technical scheme, a kind of method of fuel cell pile activation of the present invention includes the following steps:
(1) pre-activate operates:
(a) fuel electrode of Xiang Suoshu fuel cell supplies fuel, and air electrode supplies air, and adjusts single battery
Open-circuit voltage V4For 0.95~1.2V, continue 2~8min；
(b) the gas supply for stopping fuel electrode, air electrode, is passed through humidified nitrogen to fuel cell the two poles of the earth, nitrogen is blown
Pile is swept, until single battery voltage V2It is down to 0.4~0.5V；
(c) nitrogen supply (NS) for stopping two lateral electrode of fuel cell, is passed through air to fuel electrode side, air electrode side is passed through
Hydrogen continues 8~15min；
(d) the gas supply for stopping fuel electrode, air electrode, is passed through humidified nitrogen to fuel cell the two poles of the earth, nitrogen is blown
Pile is swept, until single battery voltage V3It is down to 0.4~0.5V；
(e) nitrogen supply (NS) for stopping two lateral electrode of fuel cell supplies fuel to fuel-cell fuel electrode, to air electricity
Air is supplied in pole, then loads the first current density to single battery voltage V0For 0.6~0.65V, first current density
≥1A/cm2, the V0Retention time be 25~35min；
(2) activation act is humidified:
(f) fuel cell for obtaining step (1) is in second 1.1~1.3A/cm of current density28~15min of lower activation；
(g) then stop two lateral electrode of fuel cell fuel and air supply, with third current density 0.08~
0.12A/cm2By single battery voltage V1It adjusts to 0.75~0.85V, keeps 8~15min；
(h) it is passed through air to air electrode side, fuel electrode side is passed through fuel, by fuel cell in the 4th current density
0.1~1.2A/cm2Variation △ V, the △ V > 10mV of the single battery voltage in 15~20min of time are tested in lower operation,
Repeat step (2), until the △ V≤10mV, completes fuel cell pile activation, the fuel cell pile activation
In the process, the humidified nitrogen relative humidity being passed through is 70%~100%, and the relative air humidity being passed through is 70%~100%, is led to
The fuel relative humidity entered is 70%~100%, and the temperature of activation process is 55~65 DEG C.
Compared with the existing technology, the invention has the following advantages:
(1) present invention makes the quick shape of electrode surface by once prewet activation and the secondary activation process of prewetting of pile first
At short time high potential, and then the unstable catalyst and oxidizing electrode surface impurity of electrode surface are eliminated, realizes membrane electrode
Quickly activation；Then pass through the humidification activation process of time-dependent current, run under high current density, the water that reaction can be made to generate increases rapidly
Wet film electrode realizes the quick humidification of proton exchange membrane, Catalytic Layer resin；By controlling pile in the friendship of high and low current density
Difference operation, can make electrode quickly form stable gas, electron propagation ducts, realize the acceleration activation of fuel cell pile.
(2) activation process of the present invention is simple, and activation time can control within 2h, minimum up to 1.5h, meets batch
The demand that metaplasia produces, and the fuel cell that activation obtains has good chemical property.
Detailed description of the invention
Fig. 1 is the polarization curve and power density curve graph of fuel cell pile activation front and back in the embodiment of the present invention 1；
Fig. 2 is the polarization curve and power density curve graph of fuel cell pile activation front and back in the embodiment of the present invention 2；
When Fig. 3 is that fuel cell pile activation is completed in the embodiment of the present invention 2, stable average unit voltage-time is bent
Line chart；
Fig. 4 be comparative example 1 of the present invention in fuel cell pile activate 1.5 hours with activate 2 hours after polarization curve and
Power density curve graph；
Fig. 5 is the polarization curve and function that fuel cell pile activates 1.5 hours with activation 2 hours in comparative example 2 of the present invention
Rate densogram.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
A kind of method of fuel cell pile activation includes the following steps:
(1) pre-activate operates:
(a) hydrogen that the fuel electrode supply relative humidity of Xiang Suoshu fuel cell is 80%, air electrode supply are opposite
Humidity is 80% air, and adjusts the open-circuit voltage V of single battery4For 1V, continue 5 minutes；
(b) the gas supply for stopping fuel electrode, air electrode, being passed through relative humidity to fuel cell the two poles of the earth is 80%
Humidified nitrogen, nitrogen purges pile, until single battery voltage V2It is down to 0.45V；
(c) nitrogen supply (NS) for stopping two lateral electrode of fuel cell is passed through the air that humidity is 80% to fuel electrode side, empty
Gas electrode side is passed through the hydrogen that relative humidity is 80%, continues 10 minutes；
(d) the gas supply for stopping fuel electrode, air electrode, being passed through relative humidity to fuel cell the two poles of the earth is 80%
Humidified nitrogen, nitrogen purges pile, until single battery voltage V3It is down to 0.45V；
(e) nitrogen supply (NS) for stopping two lateral electrode of fuel cell, each leads into relative humidity to fuel cell electrode two sides
Then the hydrogen that air and relative humidity for 80% are 80% loads the first current density to single battery voltage V0For
0.62V, first current density are 1.2A/cm2, the V0Retention time be 30min；
(2) activation act is humidified:
(f) fuel cell for obtaining step (1) is in the second current density 1.2A/cm2Lower activation 10min；
(g) stop the fuel and air supply of two lateral electrode of fuel cell, then with third current density 0.1A/cm2It will
Single battery voltage V1It adjusts to 0.8V, keeps 10min；
(h) it is passed through air to air electrode side, fuel electrode side is passed through fuel, by fuel cell in the 4th current density
1A/cm2Lower operation tests variation △ V, the △ V > 10mV of the single battery voltage in time 20min and repeats step
(2) until △ V≤10mV, completes fuel cell pile activation, the temperature of fuel cell pile activation process is 60 DEG C.
In the present embodiment fuel cell pile activation front and back polarization curve and power density curve graph as shown in Figure 1, by
As can be seen that Performance data is significantly improved after activation in figure.
Embodiment 2
A kind of method of fuel cell pile activation includes the following steps:
(1) pre-activate operates:
(a) hydrogen that the fuel electrode supply relative humidity of Xiang Suoshu fuel cell is 85%, air electrode supply are opposite
Humidity is 85% air, and adjusts the open-circuit voltage V of single battery4For 1.1V, continue 6 minutes；
(b) the gas supply for stopping fuel electrode, air electrode, being passed through relative humidity to fuel cell the two poles of the earth is 85%
Humidified nitrogen, nitrogen purges pile, until single battery voltage V2It is down to 0.47V；
(c) nitrogen supply (NS) for stopping two lateral electrode of fuel cell is passed through the air that humidity is 85% to fuel electrode side, empty
Gas electrode side is passed through the hydrogen that relative humidity is 85%, continues 10 minutes；
(d) the gas supply for stopping fuel electrode, air electrode, being passed through relative humidity to fuel cell the two poles of the earth is 85%
Humidified nitrogen, nitrogen purges pile, until single battery voltage V3It is down to 0.46V；
(e) nitrogen supply (NS) for stopping two lateral electrode of fuel cell, each leads into relative humidity to fuel cell electrode two sides
Then the hydrogen that air and relative humidity for 85% are 85% loads the first current density to single battery voltage V0For
0.61V, first current density are 1.3A/cm2, the V0Retention time be 28min；
(2) activation act is humidified:
(f) fuel cell for obtaining step (1) is in the second current density 1.3A/cm2Lower activation 9min；
(g) stop the fuel and air supply of two lateral electrode of fuel cell, then with third current density 0.1A/cm2It will
Single battery voltage V1It adjusts to 0.8V, keeps 10min；
(h) fuel cell for obtaining step (1) is in the second current density 1.2A/cm2Lower activation 10min；
(i) stop the fuel and air supply of two lateral electrode of fuel cell, then with third current density 0.1A/cm2It will
Single battery voltage V1It adjusts to 0.8V, keeps 10min；
(j) it is passed through air to air electrode side, fuel electrode side is passed through fuel, by fuel cell in the 4th current density
1A/cm2Lower operation tests variation △ V, the △ V > 10mV of the single battery voltage in time 20min and repeats step
(2) until △ V≤10mV, completes fuel cell pile activation, the temperature of fuel cell pile activation process is 60 DEG C.
In the present embodiment fuel cell pile activation front and back polarization curve and power density curve graph as shown in Fig. 2, by
As can be seen that Performance data is significantly improved after activation in figure；When fuel cell pile activation is completed, stable average single pond
Voltage-time curve figure is as shown in figure 3, as can be seen from Figure, the average voltage △ V of pile is less than or equal within 20 minutes
5mV, it was demonstrated that by step described in embodiment 2, pile completes activation act.
Comparative example 1
The difference from embodiment 1 is that without step (b), i.e., without activation of once prewetting.
In the present embodiment fuel cell pile activate 1.5 hours with activation 2 hours after polarization curve and power density song
Line chart is as shown in figure 4, as can be seen from Figure, if pile is after activation 1.5 hours, Performance data without step (b)
And not up to highest exports；Continue activation 0.5 hour, Performance data is still improving.Prove that step (b) activates to pass pile
It is important.
Comparative example 2
The difference from embodiment 1 is that without step (c).
In the present embodiment fuel cell pile activate 1.5 hours with activation 2 hours after polarization curve and power density song
Line chart is as shown in figure 5, as can be seen from Figure, if pile is after activation 1.5 hours, Performance data without step (c)
And not up to highest exports；Continue activation 0.5 hour, Performance data is still improving.Prove that step (c) activates to pass pile
It is important.
Comparative example 3
It is comparative example with embodiment 1 in CN105895938B, includes the following steps:
Step 1: Proton Exchange Membrane Fuel Cells is placed on test platform, and cathode is passed through humidification nitrogen, and anode is passed through increasing
Wet hydrogen checks Proton Exchange Membrane Fuel Cells air-tightness；
Step 2: setting battery operating temperature is 70 DEG C；
Step 3: after Proton Exchange Membrane Fuel Cells reaches setting temperature, cathode nitrogen and anode hydrogen gas are persistently kept
It is passed through 2h；Hydrogen flow rate is 500mL/min, nitrogen flow rate 500mL/min；
Step 4: by cathode be passed through gas be converted to humidification oxygen and/or air, oxygen and/or air velocity be
500mL/min carries out polarization performance test to the Proton Exchange Membrane Fuel Cells or cyclic voltammetry is tested 6 times, again will
Cathode is passed through gas and is converted to humidification nitrogen, and keeps 15min；
Step 5: repeating step 3 and step 4 10 times, until the Proton Exchange Membrane Fuel Cells polarization performance keeps steady
It is fixed.Whole activation time is 8h.
Performance test:
Fuel cell after activation is performed the following performance tests:
(1) activation time: the total time of the record entire activation process of fuel cell；
(2) fuel cell that the present invention uses is 180cm for 25 economize on electricity chemistry active areas2Pem fuel electricity
Pond pile is placed in fuel battery test platform frame by the pile without overactivation and using the pile after the activation of the application method,
Electrochemical property test is carried out at room temperature, and test result is as shown in Figs. 1-5.
Table 1
| Activation time (h) | |
| Embodiment 1 | 1.5 |
| Embodiment 2 | 1.7 |
| Comparative example 1 | 2.0 |
| Comparative example 2 | 2.0 |
| Comparative example 3 | 8 |
It can be seen from Table 1 that the activation time of the application can control within 2 hours, and it is minimum up to 1.5h, meet
The demand of mass production.
Method detailed of the invention that the present invention is explained by the above embodiments, but the invention is not limited to it is above-mentioned in detail
Method, that is, do not mean that the invention must rely on the above detailed methods to implement.Person of ordinary skill in the field should
It is illustrated, any improvement in the present invention, addition, the concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention
Selection etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of method of fuel cell pile activation, which is characterized in that described method includes following steps:
(1) once prewet activation and secondary activation of prewetting are carried out to fuel cell the two poles of the earth, then loads the first current density to film
Electrode activates voltage V0；
Described once prewet between activation and secondary activation of prewetting further includes generating the process of water in two side reaction of electrode；
(2) fuel cell that step (1) obtains is activated under the second current density, it is then with third current density that single-unit is electric
Cell voltage is adjusted to V1, the third current density < the second current density；
(3) fuel cell that step (2) obtains is run under the 4th current density, tests single battery voltage in time T
Variation △ V.
2. the method as described in claim 1, which is characterized in that further include being pre-processed to fuel cell before step (1)
Process；
Preferably, the preprocessing process includes: to supply fuel to the fuel electrode of the fuel cell, and air electrode supply is empty
Gas, and adjust the open-circuit voltage V of single battery4For 0.95~1.2V, continue 2~8min.
3. method according to claim 1 or 2, which is characterized in that step (1) process of activation of once prewetting includes:
It is passed through humidified nitrogen to fuel cell the two poles of the earth, nitrogen purges pile, until single battery voltage V2≤0.5V；
Preferably, the V2For 0.3~0.5V, preferably 0.4~0.5V；
Preferably, the time of the activation of once prewetting is 8~15min.
4. the method as described in one of claim 1-3, which is characterized in that step (1) is described to generate water in two side reaction of electrode
Process include: two lateral electrodes after stopping once prewetting activation nitrogen supply (NS), be passed through air to fuel electrode side, air electricity
Pole side is passed through hydrogen, continues 8~15min；
Preferably, the fuel includes hydrogen.
5. the method as described in one of claim 1-4, which is characterized in that the process packet of step (1) the secondary activation of prewetting
It includes: being passed through humidified nitrogen to fuel cell the two poles of the earth, nitrogen purges pile, until single battery voltage V3≤0.5V；
Preferably, the V3For 0.3~0.5V, preferably 0.4~0.5V；
Preferably, described two times for prewetting activation were 8~15min.
6. the method as described in one of claim 1-5, which is characterized in that after step (1) the secondary activation of prewetting, load
It further include the nitrogen supply (NS) of two lateral electrodes after stopping secondary activation of prewetting, then to air electrode before first current density
Side is passed through air, and fuel electrode side is passed through the process of fuel；
Preferably, step (1) first current density >=1A/cm2, preferably 1~1.5A/cm2；
Preferably, step (1) membrane electrode activates voltage V0For the voltage of single battery, preferably 0.6~0.65V；
Preferably, step (1) V0Retention time >=20min, preferably 25~35min.
7. the method as described in one of claim 1-6, which is characterized in that step (2) second current density be 1~
1.5A/cm2, preferably 1.1~1.3A/cm2；
Preferably, the time activated under second current density is 8~15min；
It preferably, further include the fuel and air for stopping two lateral electrode of fuel cell after being activated under second current density
The process of supply；
Preferably, the third current density is 0.05~0.15A/cm2, preferably 0.08~0.12A/cm2；
Preferably, the V1>=0.7V, preferably 0.7~0.9V, further preferably 0.75~0.85V.
8. the method as described in one of claim 1-7, which is characterized in that step (3) described fuel cell is close in the 4th electric current
It further include that air is passed through to air electrode side, fuel electrode side is passed through the process of fuel before the lower operation of degree；
Preferably, the 4th current density is 0.1~1.2A/cm2；
Preferably, the time T is 15~20min；
Preferably, the △ V≤10mV completes fuel cell pile activation；
Preferably, the △ V > 10mV repeats step (2) and step (3), until the △ V≤10mV.
9. method as described in one of claim 1-8, which is characterized in that the total time of the fuel cell pile activation process
For 1.5~2.5h；
Preferably, the temperature of the fuel cell pile activation process is 55~65 DEG C；
Preferably, during the fuel cell pile activation, the humidified nitrogen relative humidity being passed through is 70%~100%；
Preferably, during the fuel cell pile activation, the relative air humidity being passed through is 70%~100%；
Preferably, during the fuel cell pile activation, the fuel relative humidity being passed through is 70%~100%.
10. method as claimed in one of claims 1 to 9, which is characterized in that described method includes following steps:
(1) pre-activate operates:
(a) fuel electrode of Xiang Suoshu fuel cell supplies fuel, and air electrode supplies air, and adjusts the open circuit of single battery
Voltage V4For 0.95~1.2V, continue 2~8min；
(b) the gas supply for stopping fuel electrode, air electrode is passed through humidified nitrogen, nitrogen purging electricity to fuel cell the two poles of the earth
Heap, until single battery voltage V2It is down to 0.4~0.5V；
(c) nitrogen supply (NS) for stopping two lateral electrode of fuel cell, is passed through air to fuel electrode side, air electrode side is passed through hydrogen
Gas continues 8~15min；
(d) the gas supply for stopping fuel electrode, air electrode is passed through humidified nitrogen, nitrogen purging electricity to fuel cell the two poles of the earth
Heap, until single battery voltage V3It is down to 0.4~0.5V；
(e) nitrogen supply (NS) for stopping two lateral electrode of fuel cell is supplied fuel to fuel-cell fuel electrode, is supplied to air electrode
Air is answered, then loads the first current density to single battery voltage V0For 0.6~0.65V, first current density >=1A/
cm2, the V0Retention time be 25~35min；
(2) activation act is humidified:
(f) fuel cell for obtaining step (1) is in second 1.1~1.3A/cm of current density28~15min of lower activation；
(g) stop the fuel and air supply of two lateral electrode of fuel cell, then with 0.08~0.12A/cm of third current density2
By single battery voltage V1It adjusts to 0.75~0.85V, keeps 8~15min；
(h) be passed through air to air electrode side, fuel electrode side is passed through fuel, by fuel cell the 4th current density 0.1~
1.2A/cm2Variation △ V, the △ V > 10mV of the single battery voltage in 15~20min of time are tested in lower operation, repeat into
Row step (2), until the △ V≤10mV, completes fuel cell pile activation, the process of the fuel cell pile activation
In, the humidified nitrogen relative humidity being passed through is 70%~100%, and the relative air humidity being passed through is 70%~100%, is passed through
Fuel relative humidity is 70%~100%, and the temperature of activation process is 55~65 DEG C.
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