CN1713430A - Fuel cell aging method and apparatus - Google Patents
Fuel cell aging method and apparatus Download PDFInfo
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- CN1713430A CN1713430A CNA2005100775805A CN200510077580A CN1713430A CN 1713430 A CN1713430 A CN 1713430A CN A2005100775805 A CNA2005100775805 A CN A2005100775805A CN 200510077580 A CN200510077580 A CN 200510077580A CN 1713430 A CN1713430 A CN 1713430A
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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
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Abstract
Provided are an aging method and an aging device of a fuel cell capable of shortening aging time, decreasing a manufacturing cost, and facilitating aging after incorporation in an appliance. The aging method of the fuel cell is that an anode medium 6A such as a methanol aqueous solution is supplied to an anode 3A of the fuel cell requiring aging, such as a direct methanol fuel cell, a cathode medium 6B such as air is supplied to a cathode 3B, and forced current flow is conducted between the anode 3A and the cathode 3B in the same direction as the current flow in the power generation of the fuel cell.
Description
Technical field
The present invention relates to a kind of aging method and aging equipment of fuel cell, particularly move and portable power supplies, used for electric vehicle power supply, family in the aging method and the aging equipment of employed direct methanol fuel cell such as cogeneration system.
Background technology
Recently, from viewpoints such as earth environment protections, the expectation of fuel cell is just sharply raise.Fuel cell generally can be divided into according to dielectric kind of using: 5 kinds of Solid Oxide Fuel Cell (SOFC), molten carbonate fuel cell (MCFC), alkaline fuel cell (AFC), phosphoric acid fuel cell (PAFC), solid polymer fuel cell (PEFC).
Wherein, have 2 kinds of electrodes of use and sandwich solid polymer membrane, and clamp the solid polymer fuel cell (being called " PEFC " below the Polymer Electrolyte Fuel Cell) of the structure of these parts except compact generating efficiency height with separator, also can under lower temperature, work, so have wide range of applications, get most of the attention.
In addition, recently in PEFC, except hydrogen is acted as a fuel, the methanol aqueous solution direct methanol fuel cell of using (Direct Methanol Fuel Cell is hereinafter referred to as " DMFC ") that directly acts as a fuel is gained a special interest.DMFC produces electric power by making the fuel that contains the first alcohol and water, the oxidant gas generation electrochemical reaction that contains oxygen such as air, owing to work at normal temperatures and can miniaturization and sealingization, so can use in non-harmful automobile, home-use electricity generation system, mobile communicating device, medicine equipment etc., its application is a lot.
The basic structure of DMFC is: as unit cells (hereinafter referred to as " battery "), and the laminate of conductivity separator that constituted lamination in the both sides of flat electrode structural body (being called " MEA " below the Membrance Electrode Assembly).。MEA is a 3-tier architecture of clamping the dielectric film that is made of ion exchange resin etc. between the 1 pair of electrode that constitutes anode electrode and cathode electrode.1 pair of electrode is respectively by constituting with the fuel in the dielectric film electrodes in contact catalyst layer and the electrode catalyst layer outside or the diffusion layer (dispersion layer) of oxidant gas.Lamination conductivity separator makes it contact with the diffusion layer (dispersion layer) of MEA, and form the shunt hole work as path, the purpose of above-mentioned path be fuel or oxidant to the adjustment of the inflow of diffusion layer (dispersion layer), separator, remove effluent etc.By such fuel cell, for example the mixed solution by flowing through methyl alcohol and water in the shunt hole that joins at diffusion layer with anode electrode, in the shunt hole that the diffusion layer (dispersion layer) with cathode electrode joins, flow through oxidizing gas such as oxygen or air, cause that electrochemical reaction produces.
In DMFC, because the power generation characteristics after the fuel cell assembling just is very low and unstable, so usually under the situation of DMFC battery, after battery assembling, under the temperature higher, (common 60～80 ℃) carry out 3～40 hours generating than room temperature as initial stage adaptability running (below be called aging) needs.Thus, show the battery output higher than the power generation characteristics after the firm assembling.
As this aging problem points, the 1st because for aging running needs generating for a long time, so the cost when causing the volume production fuel cell increases.The 2nd, the aging condition behind the fuel cell of packing in machine is restricted.
As the method for the ageing time that shortens solid polymer fuel cell, for example the aging method of record is known in patent documentation 1.
In the patent documentation 1 publicity have the method for operation of the fuel cell of following feature: have the solid polymer membrane of bringing into play the conductivity of fuel ion by water conservation, as in the monomer at this fuel cell overflow (flooding) taking place when the elimination run of fuel cell, promote the utilance of institute's spent gas.
The purport of recording and narrating in patent documentation 1 is: according to this structure, give solid polymer membrane by the overflow that takes place with moisture, because the water content of solid polymer membrane rises, suitably form 3 bed boundarys, reach the promotion elimination run and shorten its required time.
(patent documentation 1) spy opens communique 2003-No. 217622
But the aging method of the fuel cell of patent documentation 1 is difficult to deserve to be called and solves above-mentioned aging problem fully.
Summary of the invention
Therefore, the object of the present invention is to provide a kind of aging method of fuel cell and this aging equipment, can easily realize shortening ageing time, reduce aging behind the manufacturing cost and the machine of packing into by easy method.
The present invention in order to achieve the above object, a kind of aging method of fuel cell is provided, it is characterized in that, anode electrode to fuel cell is supplied with the pure water or the aqueous solution, cathode electrode to described fuel cell is supplied with the gas that contains aerobic, forces energising in the identical direction of the energising to fuel cell power generation time the between described electrode.
The comparatively ideal form of the present invention has following feature,
1) described pressure energising uses DC power supply to carry out.
2) described pressure energising is with 150～3000mA/cm
2Current density in the scope is switched on.
3) described pressure energising uses AC power to carry out.
4) described pressure energising is that electrode structural body (MEA) temperature at described fuel cell reached before 100 ℃, perhaps applies voltage in the maximum of each monomer of described fuel cell and switches on before reaching 3V.
5) the described gas that contains aerobic is pure oxygen, air or the nitrogen that contains oxygen 0.001～1%.
6) described fuel cell is DMFC.
The present invention provides a kind of aging equipment in order to achieve the above object, it is characterized in that possessing: have the fuel cell that anode electrode and cathode electrode need wear out; Be used for supplying with pure water or the aqueous solution, supplying with the aging medium feed unit of the gas that contains aerobic to described cathode electrode to described anode electrode; Apply the voltage applying unit that is used for forcing the voltage of switching in the identical direction of the energising to described fuel cell power generation time the between described electrode; Control unit with the control of carrying out described aging medium feed unit and described voltage applying unit.
In the comparatively ideal form of the present invention, have and above-mentioned 1)～6) identical feature.
According to aging method of the present invention and aging equipment thereof, can realize easy aging, shorten the aging time, relax aging condition, and reduce the cost of fuel cells by these.In addition, can easily realize packing into aging behind the machine.
Description of drawings
Fig. 1 is the summary construction diagram that expression relates to the aging equipment of embodiment of the present invention.
Fig. 2 is a schematic diagram of implementing electric current one voltage curve when aging of the present invention.
Fig. 3 is that the time diagram when aging of the present invention is implemented in expression.
Embodiment
Below, with reference to accompanying drawing embodiments of the present invention are described, but the present invention is not limited only to this.
(overall structure of aging equipment of the present invention)
Fig. 1 relates to the summary construction diagram of the aging equipment of embodiment of the present invention.The general configuration of this aging equipment 10 has: the DMFCl of aging object; Electric field applying unit 11 is as DMFCl being applied voltage and making the electric field of current flowing give the unit; The control unit 12 of control voltage applying unit 11.In addition, DMFCl both can be with one such as voltage applying units 11, also can be to separate.In addition, describe at this DMFC to particular significant effect, but if need aging fuel cell the present invention also can be suitable for, not restriction especially here.Comparatively ideal is to be applicable to solid polymer fuel cell, is specially adapted to DMFC.
(each bilge construction of aging equipment of the present invention)
DMFCl, well-known DMFC can be suitable for, and monomer whose possesses: anode-side separator 2A and cathode side separator 2B, anode electrode 3A and cathode electrode 3B, dielectric film 4.Constitute MEA5 by anode electrode 3A, cathode electrode 3B and dielectric film 4, the both sides of clamping MEA5 with anode-side separator 2A and cathode side separator 2B.Cooperate with the purpose electromotive force, DMFCl generally adopts the structure with a plurality of monomer series-connected connections.
Anode electrode 3A and cathode electrode 3B are made of the supporting layer of supply that is used for fuel or oxidant gas and diffusion (dispersion) and the catalyst layer of generation oxidation or reduction reaction respectively.Pass through the oxidation reaction of the first alcohol and water of supply on anode electrode 3A, generate hydrogen ion, electronics and carbon dioxide, the hydrogen ion of generation is delivered to cathode electrode 3B by dielectric film 4, and the electronics of generation is delivered to cathode electrode 3B by external circuit.Reduction reaction by hydrogen ion and oxygen on cathode electrode 3B generates water.
Solid polymer membrane to dielectric film 4 does not limit especially, but for example can use the film (thickness 50～100 μ m) with the perfluorocarbon sulfone acid structure that contains the sulfonation acidic group as ion-exchange group, can make small-sized battery.
Anode-side separator 2A has formed the fuel supply groove that is used for to the anode electrode 3A of adjacency fueling, separator 2B has formed the oxidant gas supply groove that is used for supplying with to the cathode electrode 3B of adjacency oxidant gas, along separator 2A, 2B surface, fueling, oxidant gas.
Do not limited especially as separator 2A, 2B, but for example can suitably use carbon separation unit, to resin add the synthetic casting mold separator of the carbon of carbon, have titanium on the surface, stainless steel or with the apparatus for separating metals of noble metal as the anti-corrosion layer of representative.
Voltage applying unit 11 applies voltage according to the instruction from control unit 12 to DMFCl, forces energising.It is desirable using DC power supply, but also can use AC power.In addition, control unit 12 possesses CPU etc., carries out the control of aging method described later.
(aging method of the present invention)
Secondly, the aging method that relates to embodiment of the present invention is described.
Implement following step as aging method.
1. supply with anode medium 6A to the anode electrode 3A of DMFCl, supply with negative electrode medium 6B to cathode electrode 3B.In addition, supply method can be a forced circulation, also can be the method for supplying with spontaneous current.
2. prepare DC power supply (voltage applying unit 11), with the anode electrode 3A of DMFCl and the anodal line of DC power supply output, with the cathode electrode 3B of DMFCl and the negative pole line of DC power supply output.The electric current of equidirectional is switched on forcibly to MEA5 in the time of can making with common generating by such line.In addition, also can use AC power.
3. use DC power supply that DMFCl is forced energising.Power on condition is that the current density, J e of unit electrode surface area of MEA5 is at 150～3000mA/cm
2Electric current in the scope, the voltage between terminals of establishing each monomer of DMFCl is 0.3～3V, conduction time from the several seconds was by several minutes.In addition, also can use smaller or equal to the AC power of ± 3000mA/cm2 and switch on.In energising, antianode is supplied with so that it can have moisture.By repeatedly repeating these, the aging end of DMFCl.
Below, the aging method that relates to embodiment of the present invention is illustrated in greater detail.
1) anode medium 6A
In anode medium 6A, make water or methanol aqueous solution.In the generating of the DMFC of reality,, be preferably so fill the methanol aqueous solution of this concentration range because the concentration of employed methyl alcohol is 0.1～10mol/L.On the other hand, even use pure water after the pressure energising that is used to wear out, if, when forcing energising, also can use pure water for DMFC generating running exchanges to methanol aqueous solution, but, preferably use methanol aqueous solution commonly used to act as a fuel in order to save time, the time of clearing house cost.In addition, consider the electrolysis of water, key element of the present invention is not limited only to water and methanol aqueous solution, also can be the aqueous solution that anode medium 6A does not injure MEA5.For example, can be ethanol water, isopropanol water solution etc.As supply method have anode electrode 3A be provided with the aqueous solution water tank method and supply with the method etc. of solution with forced circulation, there is no particular limitation.In addition, except the synthetic also relevant with key element of the present invention of water considered in the electrolysis of water, effect of the present invention is proved effective by both composite action.
2) negative electrode medium 6B
Supply with gas, for example air (nitrogen that contains aerobic) that contains aerobic at negative electrode medium 6B.There is no particular limitation for the content of oxygen, and high concentration that purity oxygen is such or 0.001～1% low concentration can.Just can use if contain the gas of aerobic, can select the kind/concentration of the gas that contained beyond oxygen concentration, the oxygen from viewpoints such as easy row, economy.As supply method, have the method that the structure of the general breathing type DMFC by placing cathode electrode 3B etc. in atmosphere is supplied with, the method for perhaps coming supply gas with forced circulation, there is no particular limitation.
3) the current density, J e of pressure energising
In the DMFC of reality generating, usually at 0～200mA/cm
2Scope in the running of generating electricity.In forcing energising, need carry out electric current energising more than or equal to load current density contemplated in the DMFC of reality generating, use current density at 150～3000mA/cm
2It is preferably that electric current in the scope is forced energising.Be more preferably 250～2000mA/cm
2, that better is 350～1500mA/cm
2, that best is 400～1400mA/cm
2When current density is too small, just do not have effect, then become the reason that causes the MEA5 heat damage when excessive.More than or equal to 2500mA/cm
2The time in order to prevent the heat damage of MEA5, comparatively ideal is that one side is cooled off monomer or shortened conduction time (for example, shortening to the several seconds) one side and force energising.Using the current value in above-mentioned scope from viewpoints such as conveniences is preferably with certain electric current pressure energising.
When using AC power, with current density at ± 3000mA/cm
2It is preferably that electric current in the scope is forced energising.Be more preferably ± 2000mA/cm
2In the scope, better is ± 1500mA/cm
2In the scope, best is ± 1400mA/cm
2In the scope.
In addition, even current density is little, by increasing conduction time, increasing the number of times of switching on again and also can improve effect of the present invention.
That 4) forces energising applies voltage V
In the energising, applying the voltage that is equivalent to 0.3～3V is preferably as the inter-electrode voltage of each monomer.Be more preferably 0.6～2.7V, that better is 0.9～2.5V.So because the effect that wears out can't take place almost to can not get in electrolysis when voltage is too small.When voltage is excessive owing to cause that so fire damage or electric injury also are unfavorable.
5) force the t and energising number of times conduction time of energising
Comparatively ideal be the several seconds～switch between several minutes.When conduction time is too short, almost can not get effect.And temperature rising and the separator owing to heating MEA5 carries out electrochemical reaction (for example, corrosion) so also be unfavorable when the time is long.As suitable conduction time the temperature at MEA5 reached before 100 ℃, the maximum voltage of each monomer when perhaps certain electric current is forced energising is switched on before reaching 3V, electrical current is set to zero then.Repeating 2～6 such operations is preferably.Be more preferably 3～5 times.When repeating to switch on, the voltage when the previous energising of voltage ratio in when beginning energising begins is low, but comparatively ideal be before almost reducing, not carry out, be more preferably before undiminished last taking second place and switch on again.Both, repeating to switch on again till the internal resistance of monomer is stable is preferably.For example, if the voltage the when energising of the 3rd time and the 4th begins about equally, finishing aging by 3 times pressures energisings is preferably.
6) as above-mentioned 3)～5) the conditional decision method that applies voltage V, electrical current I (current density, J e), conduction time t, be wherein a kind of method according to following flow process.
A) when aging, the metering monomer apply voltage V, electrical current I, monitor V-I characteristic simultaneously.
B) increase electric current and voltage (Fig. 2) with DC power supply.
C) below electric current one voltage regime (hereinafter referred to as " appropriate area ") of the point (at Fig. 2, before and after the 10A) that the dV/dI of current/voltage sharply increases along with electric current increase and beginning, carry out the pressure of certain electric current and switch on.Fig. 2 is a schematic diagram of implementing the electric current-voltage curve when aging of the present invention, forces to switch on certain electric current of about 10A.In addition, the enforcement of adjustment by forcing conduction time or cooling processing can be suitable for the electric current-voltage regime (hereinafter referred to as " overcurrent zone ") above appropriate area.
D) temperature as MEA5 reaches 70～100 ℃, when the maximum voltage of each monomer when perhaps certain electric current is switched on is increased to 1～3V, finishes energising.If be t the conduction time of this moment
1
E) temperature of confirming MEA5 is carried out above-mentioned c once more below 50 ℃ or lower than the temperature after the energising just) and operation d).Energising is carried out 3～6 times again.In order to shorten the stand-by period, also can force cooling.The temperature of MEA5 when begin according to switching on conduction time again again is different and different.
7) replace above-mentioned 6) c), d) the conditional decision method that applies voltage V, electrical current I (current density, J e), conduction time t, use satisfy V, the I of following formula (1)～(3), the value of t is switched on, and also is one of method.
Δ T＜100 ... formula (1)
T
2＜100 ... formula (2)
Q＜100 ... formula (3)
Δ T=(V
1+ V
2) ÷ 2 * I * t ÷ (C
2P
2V
a) ... formula (4)
Q=V * I ÷ S (W/cm
2) ... formula (5)
And,
Δ T: the estimate that the temperature that is caused by energising rises (℃)
T
1: the temperature of the MEA5 before the energising (℃)
T
2: the temperature of the MEA5 after energising has just finished (℃)
V
1: apply voltage after using the energising of certain electric current just to begin
V
2: use the energising of certain electric current will finish the preceding voltage that applies
C
2: anode injects the specific heat (J/ (gK)) of liquid
P
2: anode injects density of liquid (g/cm
3)
V
a: the anode of each MEA injects liquid measure (cm
3/ sec)
Electrode surface area (the cm of S:MEA
2)
In addition, be made as in temperature T 1 under the situation of room temperature (25～30 ℃) MEA5, Δ T＜60～70th, preferably.
If Δ T (℃)＜the 100th, because T1＞0, the maximum temperature of MEA5 is no more than 100 ℃.If q is (W/cm
2)＜the 100th is because as q＞100W/cm
2The time interface transfer to the film boiling thermal diffusion from nuclear boiling and worsen, and because generate the electrolysis that the boiling film suppresses water, so be unfavorable in anodic interface.
DV/dI characteristic when 8) forcing energising
Be preferably with the little voltage source super-high-current that applies of trying one's best.Therefore necessarily switching on the following current value of appropriate area is preferably.
Fig. 3 is that the time diagram when aging of the present invention is implemented in expression.Certain electric current (the current density, J by above-mentioned conditional decision is used in expression
e(mA/cm
2)) situation of having carried out forcing for 3 times energising.
According to above-mentioned aging method, comparing with existing method is the short and also easy aging method of attendant equipment of time.In addition, owing to be the processing of only carrying out regulation energising, pack into aging behind the machine of DMFCl also is fine.
Concrete enforcement side example
(1) the test making of fuel cell
Making has the metal cover sheets of corrosion resistance and surface conductivity as the DMFC separator.Use stainless steel (SUS304) to make core metal, do to cover the composition metal parts of the Ti/SUS/Ti of metal with Titanium, be used to make the surface to have the surface treatment of conductivity and corrosion resistance concurrently according to enforcements such as opening in 2004-No. 158437 communiques disclosed method the spy on the surface of these parts.Use this metal parts and MEA (using Na Off イ オ Application (registered trade mark)) assembling electrode surface area S=8.4cm as dielectric film
2Monomer.
(2) force energising experiment 1
Use the monomer of assembling to force the energising experiment.Establishing anode injection liquid measure in this experiment is V
a=1 (cm
3/ sec).In addition, the specific heat water of anode injection liquid is made as C2=4.2 (J/gK) density as typical value and is made as ρ
2=1.0 (g/cm
3).
Therefore, I=electrode surface area S * electrical current density Je obtains Δ T=(V so be updated to above-mentioned formula (4)
1+ V
2) * Je * t.
Prepare DC power supply, with the anode electrode of DMFC and the anodal line of DC power supply output, with the cathode electrode of DMFC and the negative pole line of DC power supply output, the electric current energising of equidirectional when holding current density necessarily makes with common generating forcibly.In each reagent, switch on respectively 3 times.Use pure water (reagent 8) or methanol aqueous solution (0.1mol/L, 1.0mol/L, 3.0mol/L, 8.0mol/L, 10.0mol/L) (reagent 1～7,9～16) supply with solution as anode, use air (reagent 1～12), the nitrogen (reagent 13～16) that contains oxygen 0.001%～1% or pure oxygen (removing the remaining oxygen of unavoidable impurity) (reagent 17) as the negative electrode supply gas, implement by the method that makes each self-loopa forcibly.
Each reagent monomer is implemented to force energising by various conditions, use air (reagent 1～16) or pure oxygen (reagent 17) as the negative electrode supply gas down for 25 ℃ in room temperature then, carry out the evaluation of DMFC power generation characteristics with 10% negative electrode supply gas utilance.Evaluation result is showed in table 1 and table 2.Table 1 and the maximum output valve of table 2 expression by forcing power on condition and DMFC power generation characteristics to obtain.The numerical value of the maximum output valve MEA of the unit of being converted into electrode surface area.In addition, the voltage V after also expression has just begun with the energising of certain electric current
1Will finish preceding voltage V with energising
2Value.Δ T is a calculated value in table 1 and table 2, T
1, T
2It is measured value.
Secondly, monomer (the reagent X to not implementing burin-in process as a comparative example
1Negative electrode supply gas when being the evaluation of DMFC power generation characteristics is an air, reagent X
2Negative electrode supply gas when being the evaluation of DMFC power generation characteristics is a pure oxygen) and as monomer (the reagent Ys of burin-in process in 60 ℃ of following enforcement DMFC generating in 8 hours
1～Y
4When being burin-in process and the negative electrode supply gas of DMFC power generation characteristics when estimating be air, reagent Y
5Negative electrode supply gas when estimating with the DMFC power generation characteristics when being burin-in process is a pure oxygen) evaluation of the same DMFC of carrying out power generation characteristics with the foregoing description.Table 3 expression evaluation result.
[table 1]
Table 1 has a fling at the evaluation result (embodiment) of fuel cell
| Reagent N o | Force power on condition | DMFC power generation characteristics (25 ℃) | |||||
| Anode injects solution V a(mol/L) | Current density, J e(mA/cm 2) | Apply voltage V 1(V) | Apply voltage V 2(V) | T conduction time (sec) | ΔT(℃) T 1(℃) T 2(℃) | Maximum output (mW/cm 2) | |
| 1 | Methanol aqueous solution (1.0) | 150 | 0.6 | 0.7 | 200 | ΔT＝39 T 1＝30 T 2＝80 | 10 |
| 2 | Methanol aqueous solution (1.0) | 300 | 0.9 | 1.1 | 58 | ΔT＝35 T 1＝30 T 2＝70 | 20 |
| 3 | Methanol aqueous solution (1.0) | 450 | 1.2 | 1.4 | 30 | ΔT＝35 T 1＝30 T 2＝70 | 25 |
| 4 | Methanol aqueous solution (1.0) | 750 | 1.7 | 2.0 | 13 | ΔT＝36 T 1＝30 T 2＝71 | 25 |
| 5 | Methanol aqueous solution (1.0) | 105 0 | 2.0 | 3.0 | 7 | ΔT＝37 T 1＝30 T 2＝72 | 25 |
| 6 | Methanol aqueous solution (1.0) | 450 | 1.2 | 2.0 | 40 | ΔT＝58 T 1＝30 T 2＝95 | 25 |
| 7 | Methanol aqueous solution (1.0) | 450 | 1.2 | 2.4 | 45 | ΔT＝73 T 1＝30 T 2＝10 5 | 15 |
| 8 | Pure water | 450 | 1.8 | 2.2 | 30 | ΔT＝54 T 1＝30 T 2＝85 | 25 |
| 9 | Methanol aqueous solution (0.1) | 450 | 1.2 | 1.4 | 30 | ΔT＝35 T 1＝30 T 2＝70 | 25 |
| 10 | Methanol aqueous solution (10.0) | 450 | 1.2 | 1.4 | 30 | ΔT＝35 T 1＝30 T 2＝70 | 18 |
[table 2]
Table 2 has a fling at the evaluation result (embodiment) of fuel cell
| Reagent N o | Force power on condition | DMFC power generation characteristics (25 ℃) | |||||
| Anode injects solution v a(mol/1) | The close J of electric current e????(mA/cm 2) | Apply voltage V 1??(V) | Apply voltage V 2??(V) | T conduction time (sec) | ?ΔT(℃) ?T 1(℃) ?T 2(℃) | Maximum output (mW/cm 2) | |
| 11 | Methanol aqueous solution (3.0) | ????450 | ??1.2 | ??1.4 | ????30 | ?ΔT＝35 ?T 1＝30 ?T 2＝70 | 25 |
| 12 | Methanol aqueous solution (8.0) | ????450 | ??1.2 | ??1.4 | ????30 | ?ΔT＝35 ?T 1＝30 ?T 2＝70 | 25 |
| 13 | Methanol aqueous solution (1.0) ※ 1 | ????450 | ??1.2 | ??1.4 | ????30 | ?ΔT＝35 ?T 1＝30 ?T 2＝70 | 25 |
| 14 | Methanol aqueous solution (1.0) ※ 2 | ????450 | ??1.2 | ??1.4 | ????30 | ?ΔT＝35 ?T 1＝30 ?T 2＝70 | 25 |
| 15 | Methanol aqueous solution (1.0) ※ 3 | ????450 | ??1.2 | ??1.4 | ????30 | ?ΔT＝35 ?T 1＝30 ?T 2＝70 | 25 |
| 16 | Methanol aqueous solution (1.0) ※ 4 | ????450 | ??1.2 | ??1.4 | ????30 | ?ΔT＝35 ?T 1＝30 ?T 2＝70 | 25 |
| 17 | Methanol aqueous solution (1.0) ※ 5 | ????450 | ??1.2 | ??1.4 | ????30 | ?ΔT＝35 ?T 1＝3?0 ?T 2＝70 | 30 |
Reagent 13 is that the negative electrode supply gas when switching on (wearing out) with the mist of (1% oxygen+residual nitrogen) as pressure, the negative electrode supply gas when estimating as the DMFC power generation characteristics with air are implemented.
Reagent 14 is that the negative electrode supply gas when switching on (wearing out) with the mist of (0.1% oxygen+residual nitrogen) as pressure, the negative electrode supply gas when estimating as the DMFC power generation characteristics with air are implemented.
Reagent 15 is that the negative electrode supply gas when switching on (wearing out) with the mist of (0.01% oxygen+residual nitrogen) as pressure, the negative electrode supply gas when estimating as the DMFC power generation characteristics with air are implemented.
Reagent 16 is that the negative electrode supply gas when switching on (wearing out) with the mist of (0.001% oxygen+residual nitrogen) as pressure, the negative electrode supply gas when estimating as the DMFC power generation characteristics with air are implemented.
Reagent 17 is to implement with the negative electrode supply gas of pure oxygen when forcing energising (wear out) and during the evaluation of DMFC power generation characteristics.
[table 3]
Table 3 has a fling at the evaluation result (embodiment) of fuel cell
| ??No | Anode injects solution (mol/L) | The burin-in process condition | The maximum output of DMFC power generation characteristics (25 ℃) (mW/cm 2) |
| ??X 1 | Methanol aqueous solution (1.0) | No burin-in process | ????8 |
| ??X 2 | Methanol aqueous solution (1.0) | ????12 ????※6 | |
| ??Y 1 | Methanol aqueous solution (1.0) | Use air to implement 60 ℃ DMFC generating in 8 hours as the negative electrode supply gas | ????25 |
| ??Y 2 | Methanol aqueous solution (10.0) | ????18 | |
| ??Y 3 | Methanol aqueous solution (3.0) | ????22 | |
| ??Y 4 | Methanol aqueous solution (8.0) | ????20 | |
| ??Y 5 | Methanol aqueous solution (1.0) | Use air to implement 60 ℃ DMFC generating in 8 hours as the negative electrode supply gas | ????30 ????※6 |
*Negative electrode supply gas when 6 usefulness pure oxygens are estimated as the DMFC power generation characteristics is implemented
In this experiment, under the condition of Δ T=30～40, implement to force energising for the reagent of reagent 1～5.In reagent 1, can not clearly check out the generation of hydrogen in forcing energising, but in reagent 2～5, can check out the generation of hydrogen.Showed and comparison reagent Y for reagent 2～5
1Identical DMFC power generation characteristics has by forcing the aging effect of energising.About reagent 1, though frequently than reagent Y
1Low, but than the comparison reagent X of no burin-in process
1Therefore height thinks to have by forcing the aging effect of energising.In other words, the pressure power on condition of reagent 1 has been showed the lower limit of finding aging effect.
In addition,, under the condition of Δ T=58, implement to force in the energising DMFC energy output and reagent Y relatively for reagent 6
1Equate to have by forcing the aging effect of energising.On the other hand, about reagent 7, at Δ T=73 (T
2When implementing to force energising under the condition=105), the DMFC power generation characteristics after forcing to switch on is at reagent Y
1Below.Thus, consider at T
1Under the power on condition of=30 Δ T＞70, both under the power on condition of T2＞100, because the boiling of the water or the aqueous solution makes MEA worsen the decline that produces monomer functional.The upper limit of in other words, having showed burin-in process with effect in the inner condition that produces the water boiling of monomer.
Except the situation of the 1.0mol/L methanol aqueous solution of reagent 1～7, such shown in the result of reagent 8,9,10, also injecting solution at anode is under the situation of pure water, 0.1mol/L methanol aqueous solution and 10mol/L methanol aqueous solution, and forcing energising to handle DMFC power generation characteristics after (burin-in process) is suitable value (situation of 10mol/L methanol aqueous solution and reagent Y relatively
2Identical), have by forcing the aging effect of energising.
In addition, also injecting (reagent 11,12) under the situation that solution is 3mol/L and 8mol/L methanol aqueous solution and negative electrode supply gas at anode is to contain under the situation of nitrogen of oxygen 0.001%～1% (reagent 13～16), forces DMFC power generation characteristics and reagent Y relatively after energising is handled
3, Y
4Identical or more than it, recognized by forcing the aging effect of energising.
And then even using under the situation of pure oxygen as the negative electrode supply gas (reagent 17), reagent Y has been showed and compared to the comparison reagent X2 height of the no burin-in process of power generation characteristics ratio of the DMFC after forcing to handle
5Identical value has been recognized the aging effect of forcing energising.
By above result of implementation as can be known: will inject solution to the scope of 10mol/L methanol aqueous solution as anode from pure water at least, at least the scope from the nitrogen that contains aerobic 0.001% to pure oxygen can be obtained in such combination by forcing the aging effect of energising as the various combinations of negative electrode supply gas.
(3) force energising experiment 2
Use DC power supply and AC power to force the energising experiment.At first, with the anode electrode of DMFC and the anodal line of DC power supply output, with the cathode electrode of DMFC and the negative pole line of DC power supply output, the electric current energising (power-up sequence 1) of equidirectional when making forcibly with common generating.Then, line on the contrary, rightabout electric current energising (power-up sequence 2) when making forcibly with generating usually.Secondly, return initial connection state and force energising (power-up sequence 3), the line AC power replaces DC power supply to force energising (power-up sequence 4) then.And then, according to the order shown in the table 41 monomer (reagent 17) change condition is forced energising (power-up sequence 5～8) continuously.The energising number of times only the 1st time+450mA/cm
2, 30sec condition under be made as 3 times, under power on condition thereafter, be made as 1 time.Use methanol aqueous solution (1.0mol/L) to supply with solution, use air, implement by the method that makes its each self-loopa forcibly as the negative electrode supply gas as anode.Then, with " forcing energising experiment 1 " the same power generation characteristics of estimating DMFC.Evaluation result is as shown in table 4.
[table 4]
Table 4 has a fling at the evaluation result (embodiment) of fuel cell
| Power-up sequence | Force power on condition | DMFC power generation characteristics (25 ℃) | |
| Current density, J e????(mA/cm 2) | T conduction time (sec) | Maximum output (mW/cm 2) | |
| ??1 | ????+450 | ????30 | ??25 |
| ??2 | ????-450 | ????30 | ??10 |
| ??3 | ????+450 | ????30 | ??30 |
| ??4 | ????±400 | ????30 | ??30 |
| ??5 | ????-750 | ????13 | ??5 |
| ??6 | ????+750 | ????13 | ??30 |
| ??7 | ????+2000 | ????3 | ??30 |
| ??8 | ????+3000??※7 | ????20 | ??25 |
+: the direction during with common generating is identical
-: the direction during with common generating is opposite
±: exchange energising
*7: cooling implements to force energising simultaneously
According to table 4, rightabout pressure energising (power-up sequence 2,5) during with common generating, can not get effect of the present invention, if the energising of the pressure by AC power (power-up sequence 4) is because the pressure energising of equidirectional when also carrying out with generating usually, so can obtain effect of the present invention.In addition, even the current density in overcurrent zone (power-up sequence 7,8) also can be suitable for by the adjustment of forcing conduction time, the monomer cooling processing when forcing energising.
Claims (8)
1. the aging method of a fuel cell is characterized in that,
Anode electrode to fuel cell is supplied with the pure water or the aqueous solution, supplies with the gas that contains aerobic to the cathode electrode of described fuel cell, forces energising in the identical direction of the energising to fuel cell power generation time the between described electrode.
2. the aging method of fuel cell according to claim 1 is characterized in that,
Described pressure energising is to use DC power supply to carry out.
3. the aging method of fuel cell according to claim 2 is characterized in that,
Described pressure energising is with 150～3000mA/cm
2Current density in the scope is switched on.
4. the aging method of fuel cell according to claim 1 is characterized in that,
Described pressure energising is to use AC power to carry out.
5. according to the aging method of any described fuel cell in the claim 1 to 4, it is characterized in that,
Described pressure energising is that the temperature of the electrode structural body (MEA) at described fuel cell reached before 100 ℃, applies in the maximum of each monomer of described fuel cell perhaps that voltage switches on before reaching 3V.
6. according to the aging method of any described fuel cell in the claim 1 to 5, it is characterized in that,
The described gas that contains aerobic is pure oxygen, air or the nitrogen that contains oxygen 0.001～1%.
7. according to the aging method of any described fuel cell in the claim 1 to 6, it is characterized in that,
Described fuel cell is a direct methanol fuel cell.
8. an aging equipment is characterized in that,
Comprise:
Has the fuel cell that anode electrode and cathode electrode need wear out;
Be used for supplying with pure water or the aqueous solution, supplying with the aging medium feed unit of the gas that contains aerobic to described cathode electrode to described anode electrode;
Apply the voltage applying unit that is used for forcing the voltage of switching in the identical direction of the energising to described fuel cell power generation time the between described electrode; With
Carry out the control unit of the control of described aging medium feed unit and described voltage applying unit.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2004183070 | 2004-06-21 | ||
| JP2004183070 | 2004-06-21 | ||
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7903426A (en) * | 1979-05-02 | 1980-11-04 | Electrochem Energieconversie | METHOD FOR OPERATING A FUEL CELL |
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