CN109755597A - A kind of large-area flat-plate type solid oxide fuel cell palladium oxide composite cathode and preparation method thereof - Google Patents
A kind of large-area flat-plate type solid oxide fuel cell palladium oxide composite cathode and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of large-area flat-plate type solid oxide fuel cell palladium oxide composite cathode preparation methods.The present invention includes the following steps that the nano particle by palladium oxide and its stabilizer is added in previously prepared large-area flat-plate type to the cathode of solid oxide fuel cell.The present invention is on the basis of the LSM-YSZ cathode skeleton of existing solid oxide fuel cell, by injection nanoscale palladium particle as catalyst, inhibit the reunion of oxidation palladium nano-particles by stabilizer again and persistently grow up, to keep the catalytic activity and long-term working stability of nanoscale palladium beaded catalyst.The present invention can make PdO/ZrO2+ LSM-YSZ cathode has preferable chemical property and long-term working stability, significantly improves the output power of solid oxide fuel cell, is suitable for the popularization and application of large-area flat-plate type solid oxide fuel cell industrially.
Description
Technical field
The present invention relates to solid oxide fuel cell, more particularly to a kind of large-area flat-plate type solid oxide fuel
Cell oxidation palladium composite cathode and preparation method thereof.
Background technique
Solid oxide fuel cell (SOFC) be it is a kind of can by the chemical energy in fuel with efficiently, cleaning, quietly side
Formula is converted into the energy conversion device of electric energy.Traditional high temperature SOFC faces higher preparation and maintenance cost, and long-term fortune
The problems such as performance degradation during row, thus middle low temperature SOFC (IT-SOFC) becomes the emphasis studied at present.IT-SOFC tool
Have that lower cost for material, component be easy to process, long-term work steady performance.Due to operating temperature reduction and cause to pass
Unite cathode (such as La0.8Sr0.2MnO3, LSM) caused by activation loss it is excessively high, this become IT-SOFC develop difficulty urgently to be resolved
One of point.
PdO has a good application prospect in IT-SOFC as precious metal oxide catalyst, to traditional LSM yin
Pole chemical property, which has, is obviously improved effect.However PdO nano particle is easily easily reunited under high temperature and discharging condition
It grows up, cathode performance is caused to be decayed.Therefore systematically how the attenuating mechanism of research PdO injection cathode performance and exploration change
Kind long-time stability method of the PdO under IT-SOFC operating condition has the SOFC monocell for preparing high performance and long service life
Significance.
Therefore, how under high current environment guarantee PdO nano particle form stability be large-area flat-plate type solid
The key factor of oxide fuel cell.
Summary of the invention
Based on the above the deficiencies in the prior art, technical problem solved by the invention is that providing one kind can be improved solid
A kind of large-area flat-plate type solid oxide fuel cell palladium oxide composite cathode preparation method of operation of fuel cells efficiency.
The present invention realizes that above-mentioned technical purpose technical solution is as follows:
A kind of large-area flat-plate type solid oxide fuel cell palladium oxide composite cathode preparation method, including walk as follows
It is rapid:
Palladium oxide and its stabilization are injected on the cathode of previously prepared large-area flat-plate type solid oxide fuel cell
The nano particle of agent, and carry out sinter molding.
By forming the nano-particle layer of equally distributed palladium oxide and its stabilizer on the porous surface of cathode, to urge
Change chemical property and cathode performance is kept to stablize.
Further, the stabilizer is zirconium base stabilizer.
Further, the zirconium base stabilizer is YSZ or zirconium oxide.
Also further, in the cathode injection palladium oxide of the large-area flat-plate type solid oxide fuel cell and its surely
The concrete mode for determining the nano particle of agent is,
The mixed solution containing palladium oxide and its stabilizer is prepared, and the mixed solution consolidates the large-area flat-plate type
The cathode of oxide body fuel cell is sprayed.
Further, the cathode of the large-area flat-plate type solid oxide fuel cell is carried out spraying specific packet
It includes,
After the mixed solution is atomized, the mixed solution after atomization is sprayed by the big face by spraying equipment
The surface of product flat-plate-type solid-oxide fuel battery palladium oxide composite cathode；
The sinter molding specifically includes,
The large-area flat-plate type solid oxide fuel cell palladium oxide composite cathode is dried and is heat-treated,
The nanometer with nanostructure is formed in the large-area flat-plate type solid oxide fuel cell palladium oxide composite cathode skeleton
Catalyst layer.
Further, the mixed solution of the preparation containing palladium oxide and its stabilizer, specifically includes,
By PdCl2With Zr (NO3)4·5H2O or with Zr (NO3)4·5H2O and yttrium salt mixing, are added hydrochloric acid, sufficiently stir
It mixes, forms mixing salt solution；
Citric acid is added into the mixing salt solution to be added as the first complexing agent, then in the mixing salt solution
The ammonia spirit of EDTA is as the second complexing agent；
It adds ammonia spirit to the mixing salt solution pH value and rises to 7.8~8.2；The mixing salt solution is subjected to oil
Bath, stirring, evaporation water add surfactant.
Also further, the stabilizer is zirconium oxide；The PdCl2With Zr (NO3)4·5H2The molar ratio of O is 95:5
~80:20；In the mixed solution sprayed for the cathode to the large-area flat-plate type solid oxide fuel cell, oxygen
The concentration for changing palladium is 0.20~0.50mol/L, and the concentration of zirconium oxide is 0.05~0.15mol/L.
Further, the surfactant is alcohols activating agent.
Still further, the surfactant is isopropanol.
On the other hand, the invention proposes a kind of compound yin of large-area flat-plate type solid oxide fuel cell palladium oxide
Pole prepares the cathode of solid oxide fuel cell by technical solution above-mentioned.
Wherein, the nano-particle diameter of the oxidation palladium nano-particles and its stabilizer that inject on cathode is no more than 30nm.
The present invention can make PdO/ZrO2+ LSM-YSZ cathode is finally reached stabilization under 750 DEG C of operating temperatures, stablizes
Corresponding RP value and to reach the stable time be respectively 0.36 Ω cm afterwards2(165h)、0.34Ωcm2(185h) and 0.316 Ω cm2
(200h), to significantly improve the maximum output of solid oxide fuel cell.The present invention is in existing solid oxidation
On the basis of the LSM-YSZ cathode skeleton of object fuel cell, by injection nanoscale palladium particle as catalyst, then by steady
Determine agent to inhibit the reunion of oxidation palladium nano-particles and persistently grow up, to keep the catalysis of nanoscale palladium beaded catalyst living
Property and long-term working stability.The present invention can make PdO/ZrO2+ LSM-YSZ cathode has preferable chemical property and length
Phase job stability significantly improves the output power of solid oxide fuel cell, is suitable for large-area flat-plate type solid oxygen
The popularization and application of compound fuel cell industrially.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, the attached drawing to embodiment is simply situated between below
It continues.
Fig. 1 (a) is PdO/ZrO2The open circuit EIS figure of+LSM-YSZ cathode between 600 to 750 DEG C；
Fig. 1 (b) is PdO/ZrO2The Arrhenius curve of the polarization impedance of+LSM-YSZ cathode between 600 to 750 DEG C
Figure；
Fig. 2 (a) is tradition LSM-YSZ cathode in the cathode overpotential between 600 to 750 DEG C and between cathode-current density
Graph of relation；
Fig. 2 (b) is PdO/ZrO2Cathode overpotential and cathode-current density of+the LSM-YSZ cathode between 600 to 750 DEG C
Between graph of relation；
Fig. 3 (a) is PdO/ZrO2The Tafel curve graph of+LSM-YSZ cathode between 600 to 750 DEG C；
Fig. 3 (b) is exchange current density i0Arrhenius curve graph；
Fig. 3 (c) is the EIS figure under 750 DEG C and different partial；
Relational graph of the Fig. 3 (d) between polarization impedance value and partial pressure of oxygen；
Fig. 4 (a) is PdO/ZrO2+ LSM-YSZ cathode is at 750 DEG C and 400mAcm-2EIS under cathodic polarization current density
Figure；
Fig. 4 (b) is PdO/ZrO2+ LSM-YSZ cathode is at 750 DEG C and 400mAcm-2R under cathodic polarization current densityPValue
Change with time figure；
Fig. 5 is PdO/ZrO2The XRD spectrum of+LSM-YSZ composite cathode；
Fig. 6 is PdO/ZrO2, LSM-YSZ and PdO/ZrO2The O of three kinds of powders of+LSM-YSZ2- TPD curve；
Fig. 7 is SEM shape appearance figure: (a) monocell section and (b) PdO/ZrO2+ LSM-YSZ cathode；
Fig. 8 (a) is PdO/ZrO2+ LSM-YSZ cathode monocell is at 650 to 750 DEG C with H2It is oxygen for fuel gas and air
I-V-P performance curve when agent；
Fig. 8 (b) is PdO/ZrO2+ LSM-YSZ cathode monocell is at 650 to 750 DEG C with H2It is oxygen for fuel gas and air
The EIS of I-V-P when agent schemes；
Fig. 9 is PdO/ZrO2+ LSM-YSZ cathode monocell is at 750 DEG C and 400mAcm-2Under long-term discharge test voltage with
The variation of time；
Figure 10 (a) is PdO/ZrO2+ LSM-YSZ cathode monocell is at 750 DEG C and 400mAcm-20h under long-term discharge test
When EIS figure and CNLS method fitting data；
Figure 10 (b) is PdO/ZrO2+ LSM-YSZ cathode monocell is at 750 DEG C and 400mAcm-2Under long-term discharge test
The data of EIS figure and the fitting of CNLS method when 100h；
Figure 10 (c) is PdO/ZrO2+ LSM-YSZ cathode monocell is at 750 DEG C and 400mAcm-2Under long-term discharge test
The data of EIS figure and the fitting of CNLS method when 170h；
Figure 10 (d) is PdO/ZrO2+ LSM-YSZ cathode monocell is at 750 DEG C and 400mAcm-2Under long-term discharge test
The data of EIS figure and the fitting of CNLS method when 235h；
Figure 11 (a) is (a) PdO/ZrO2It is bent to scheme corresponding DRT by EIS under+LSM-YSZ cathode monocell difference electric discharge period
Line；
Figure 11 (b) is PdO/ZrO2The opposite of DRT calculated result is missed under+LSM-YSZ cathode monocell difference electric discharge period
Difference；
Figure 12 is the active balance circuit diagram of simulation, RPEach reaction step R value and and each electrode reaction institute of the value with fitting
The physical significance of representative；
Figure 13 is PdO/ZrO2+ LSM-YSZ cathode monocell is at 750 DEG C and 400mAcm-2R under testPIt is worth and fits
Six electrode reaction steps corresponding to polarization impedance value change with time relational graph；
Figure 14 (a) is PdO/ZrO2+ LSM-YSZ cathode monocell is in 750 DEG C of and 400mAcm-2In 0h, EIS figure institute is right
The data of the Bode figure and CNLS fitting answered: (a) 0h, (b) 100h, (c) 170h and (d) 235h；
Figure 14 (b) is PdO/ZrO2+ LSM-YSZ cathode monocell is in 750 DEG C of and 400mA cm-2In 100h, EIS schemes
The data of corresponding Bode figure and CNLS fitting:
Figure 14 (c) is PdO/ZrO2+ LSM-YSZ cathode monocell is in 750 DEG C of and 400mA cm-2In 170h, EIS schemes
The data of corresponding Bode figure and CNLS fitting:
Figure 14 (d) is PdO/ZrO2+ LSM-YSZ cathode monocell is in 750 DEG C of and 400mA cm-2In 235h, EIS schemes
The data of corresponding Bode figure and CNLS fitting:
Figure 15 is PdO/ZrO2+ LSM-YSZ cathode monocell is at 750 DEG C and 400mAcm-2SEM under different discharge times
Figure: (a) 100h, (b) 170h, (c) 235h and (d) PdO average particle size particle size with discharge time variation relation figure.
Specific embodiment
The embodiment of the invention will now be described in detail with reference to the accompanying drawings, and as part of this specification passes through
Embodiment illustrates the principle of the present invention, and other aspects of the present invention, feature and its advantage will become by the detailed description
It is very clear.In the attached drawing of institute's reference, the same or similar component is indicated using identical drawing reference numeral in different figures.
The present invention uses following scheme:
A kind of large-area flat-plate type solid oxide fuel cell palladium oxide composite cathode preparation method, including walk as follows
It is rapid:
Palladium oxide and its steady is injected in the cathode of previously prepared obtained large-area flat-plate type solid oxide fuel cell
Determine agent particle, and carries out sinter molding.Wherein magnesia manganese oxide etc. can be used in stabilizer.Large-area flat-plate type soild oxide
Fuel cell refers generally to area in 10cm*10cm or more, the even plate shaped battery of 15cm*15cm or more.By in cathode
Porous surface on form the nano-particle layer of equally distributed palladium oxide and its stabilizer, to promote electrochemical cathode catalytic
Can simultaneously retention property it stablize.It should be noted that keep the dredging of negative holes structure, prevent it from being blocked completely.
Preferably, stabilizer is zirconium base stabilizer.
Preferably, zirconium base stabilizer is YSZ or zirconium oxide.
The specific of palladium oxide and its stabilizer particle is injected in the cathode of large-area flat-plate type solid oxide fuel cell
Mode is
The mixed solution containing palladium oxide and its stabilizer is prepared, and by mixed solution to large-area flat-plate type soild oxide
The cathode of fuel cell is sprayed.
The mixed solution containing palladium oxide and its stabilizer is prepared, is specifically included:
By PdCl2With Zr (NO3)4·5H2O or with Zr (NO3)4·5H2O and yttrium salt mixing, are added hydrochloric acid, sufficiently stir
It mixes, forms mixing salt solution；
Citric acid complexing agent is added into mixing salt solution, then the ammonia spirit conduct of EDTA is added in mixing salt solution
Second complexing agent；
It adds ammonia spirit to mixing salt solution pH value and rises to 7.8~8.2；Mixing salt solution is subjected to oil bath, stirring,
Evaporation water adds surfactant.
Preferably, PdCl2With Zr (NO3)4·5H2The molar ratio of O is 80:20；Pd in this way and Zr meets the molar ratio of 4:1.
In the mixed solution sprayed for the cathode to large-area flat-plate type solid oxide fuel cell, the concentration of palladium oxide is
0.20~0.50mol/L, the concentration of zirconium oxide are 0.05~0.15mol/L.
When the ammonia spirit of EDTA is added as the second complexing agent in mixing salt solution, EDTA: ammonium hydroxide: citric acid rubs
The ratio between your amount is 1:1:2.
Surfactant is alcohols activating agent.
Surfactant is isopropanol.
Cathode based on the solid oxide fuel cell for preparing large-area flat-plate type through the above technical solution.
And wherein, the palladium oxide nano-particle diameter injected on cathode is not more than 30nm.
The present invention can make PdO/ZrO2+ LSM-YSZ cathode is finally reached stabilization under 750 DEG C of operating temperatures, stablizes
Corresponding RP value and to reach the stable time be respectively 0.36 Ω cm afterwards2(165h)、0.34Ωcm2(185h) and 0.316 Ω cm2
(200h), to significantly improve the output power of solid oxide fuel cell.
PdO/ZrO2The chemical property of+LSM-YSZ cathode
Fig. 1 show PdO/ZrO2Open circuit EIS figure and its polarization impedance of+the LSM-YSZ cathode between 600 to 750 DEG C
Arrhenius curve.With the raising of test temperature, PdO/ZrO2The R of+LSM-YSZ cathodePValue then correspondingly reduces from 1.68
To 0.4 Ω cm2, it is much smaller than tradition LSM-YSZ cathodic polarization impedance value；But also due to ZrO2Addition occupy the position PdO, make
Obtain PdO/ZrO2R of+LSM-YSZ the cathode at 750 DEG CPValue is slightly larger than the R of pure PdO+LSM-YSZ cathodePIt is worth (0.32 Ω cm2)。
According to the Arrhenius curve of polarization impedance value in Fig. 1 b, PdO/ZrO can be calculated2+ LSM-YSZ cathode goes back oxygen
Former reaction activity is 72.55kJ mol-1, much smaller than activation energy (the 140-163kJ mol of traditional LSM-YSZ cathode-1), it says
The addition that PdO is illustrated reduces LSM-YSZ cathode to energy barrier needed for redox reactions.
In fact, in PdO crystal structure, the 5s track of Pd ion be it is empty, be easy the independent electronic by oxygen to institute
Filling, and then coordinate bond is formed, increase its adsorption process to oxygen.Simultaneously as Pd-4d track easily with O-2p track
Antibonding hybridized phenomenon occurs, antibonding present in oxygen molecule is easy to obtain extra electron from the antibonding hydridization, so that oxygen
The O -- O bond length of molecule is increased to from 1.21To which oxygen atom be more readily formed, the dissociation process of absorption oxygen is increased, is filled
The clear PdO that defends oneself has the function of that good absorption is dissociated to oxygen.
In order to study PdO/ZrO2The redox reactions dynamic process of+LSM-YSZ cathode between 600-750 DEG C, this
Invention is tested between the overpotential (Overpotential, η) of the cathode and cathode-current density (J) using direct current polarization method
Relation curve, as shown in Figure 2.In the case where cathodic polarization electric current is constant, the overpotential of electrode the high, shows that electrode is anti-
Process is answered to need to consume progress of the energy more more than thermodynamic argument energy to drive reaction, therefore cathode overpotential is smaller, anticipates
Taste electrode electro Chemical performance it is better.It can be seen that in co-impregnation PdO/ZrO2Afterwards, PdO/ZrO2+ LSM-YSZ cathode is in phase
The overpotential of (temperature and current density) is substantially less than tradition LSM-YSZ cathode under the conditions of.For example, at 750 DEG C, traditional LSM-
YSZ cathode is 100mA cm in cathode-current density-2Under overpotential reach 434mV, and PdO/ZrO2+ LSM-YSZ cathode phase
The overpotential answered is only 80mV.LSM-YSZ cathode reaches 194mA cm in cathode-current density-2When, overpotential has reached 558mV,
And PdO/ZrO2+ LSM-YSZ cathode is 560mA cm in cathode-current density-2When, overpotential is just 530mV, is absolutely proved
PdO/ZrO2+ LSM-YSZ cathode has better ORR catalytic reaction activity.
Fig. 3 show (a) PdO/ZrO2The Tafel curve of+LSM-YSZ cathode between 600 to 750 DEG C；(b) exchanging electric current
Density i0Arrhenius curve；(c) the EIS figure under 750 DEG C and different partial and (d) polarization impedance value and partial pressure of oxygen it
Between relation curve.Pass as known to Fig. 3 a, between high polarization voltage regime, corresponding polarized current density j and overpotential η
System can be provided by formula 1:
Wherein i0For exchange current density,For apparent mass transfer coefficient, F is Faraday constant, and R is ideal gas constant, T
For thermodynamic temperature.And then exchange current density i can be calculated0Numerical value, as shown in Figure 3b.According to Arrhenius equation
(2)
A is exponential factor, E in formulaaFor the activation energy of ORR reaction.
It is found that by exchange current density i0Arrhenius curve be fitted, PdO/ZrO can be calculated2+LSM-
The activation energy about 73.3kJmol of YSZ cathode ORR reaction-1, this with before by RPThe calculated knot of relationship between value and temperature
Fruit is consistent.Fig. 3 c reflects PdO/ZrO2+ LSM-YSZ cathode is bent in the EIS figure at 750 DEG C and the relationship between partial pressure of oxygen
Line.It is found that as partial pressure of oxygen is successively reduced to 0.1,0.05atm, R from 0.21atmPValue increases to 0.55,0.77 from 0.4 respectively
Ωcm2, and low frequency arc increase it is more obvious, this with it is reported in the literature consistent about LSM-YSZ cathode characteristic.Research shows that for
The oxygen reduction reaction dynamic process of SOFC cathode, order of reaction m and exchange current density i0And partial pressure of oxygenBetween have
Following relationship (3):
And
A ' is exponential factor in formula, it is known that, RPValue and partial pressure of oxygenAnd shown in such as formula of the relationship between order of reaction m (5):
Table 1 show the basic step and its corresponding order of reaction of cathode ORR.According to Fig. 3 d, by difference
R under partial pressure of oxygenPValue is fitted, and can obtain its slope i.e. m value is 0.46, illustrates PdO/ZrO2+ LSM-YSZ cathode is unpolarized
The RDS step of preceding ORR is the oxygen dissociation process of low frequency arc, this and RPThe main contributions of value are from RPlIt is consistent to be worth result.
The basic step and its corresponding order of reaction of 1 Cathodic oxygen reduction of table
Fig. 4 show PdO/ZrO2+ LSM-YSZ cathode is at 750 DEG C and 400mAcm-2(a) EIS under polarized current density
Figure and (b) RPh、RPlWith RPValue changes with time.By being fitted using equivalent circuit (see Fig. 4 a) to EIS figure, wherein
RPhAnd RPlIt corresponds respectively to high frequency arc related with oxygen ion conduction process in EIS map and is dissociated with Oxygen Adsorption related
The impedance value of low frequency arc, CPEhWith CPElIt is then corresponding normal phase angle.In order to preferably analyze PdO/ZrO2+ LSM-YSZ yin
The ohmage value of chemical property of the pole in long-term polarization test, EIS figure is removed.It is found that when applying 400mA
cm-2When polarized current density, PdO/ZrO2+ LSM-YSZ cathode RPValue is substantially reduced, RPhWith RPlAlso occur obviously to subtract
Small, this is similar to above-mentioned PdO+LSM-YSZ cathode result, has benefited from LSM activation: i.e. the nonactive phase SrO on surface to
The diffusion of body phase enhances the Oxygen Adsorption dissociation process and Mn of low frequency arc4+Ion is reduced to Mn3+Generated Lacking oxygen increases
The strong conductive process of oxonium ion.After testing 5h, RPValue reaches 0.22 Ω cm of minimum value2, corresponding R at this timePhAnd RPlValue point
It Yue Wei not 0.01 and 0.21 Ω cm2.It can be seen that PdO/ZrO2The polarization impedance of+LSM-YSZ cathode mostlys come from low frequency arc, i.e. oxygen
The absorption dissociation process of gas is the RDS step that ORR reaction occurs for electrode.Hereafter, RPhValue starts slowly to increase, and reaches in 165h
To 0.21 Ω cm of stationary value2, and corresponding RPlValue then slowly reduces and reaches 0.15 Ω cm of stationary value in 70h2, corresponding RP
Value is then same slowly to be increased, and finally reaches 0.36 Ω cm of stationary value in 165h2。
In the polarization test of preceding 5h, still there is phenomenon of growing up in PdO particle, and will lead to the increase of polarization impedance value, but
Since activation of the polarization current to LSM-YSZ cathode is stronger, therefore mask the increasing of the impedance value as caused by PdO particle growth
Greatly.And after the polarization test of 5h, RPlIt is slow reduction illustrate polarization current still to LSM-YSZ cathode have faint activation
Effect；Growing up so that oxygen ion conduction process is obstructed and shows as R due to PdO particle at this timePhValue increases.Meanwhile it is corresponding
RPValue is in increase tendency on the whole, then illustrates that the decaying of the impedance value as caused by PdO particle growth has been more than polarization current pair
The faint activation of LSM, i.e. RPThe main contributions of value are from RPh.Compare the EIS map under initial open circuit, it is known that long-term
In polarization test, PdO/ZrO2+ LSM-YSZ cathode has been changed the RDS that ORR reacts by the Oxygen Adsorption dissociation process of low frequency arc
For the oxygen ion conduction process of high frequency arc.It is tied according to the long-term polarization of above-mentioned tradition LSM-YSZ cathode and PdO+LSM-YSZ cathode
Fruit is it is found that tradition LSM-YSZ cathode is with good stability under high temperature and polarization test；And PdO+LSM-YSZ cathode is then
It due to the reunion of PdO particle, is up to and tiles, cause its chemical property that linear attenuation occurs at any time, this is absolutely proved
PdO/ZrO2The chemical property of+LSM-YSZ cathode and long-term polarizer stability have to be promoted significantly.
For high temperature SOFC (about 1000 DEG C of operating temperature) cathode material, LSM has high electronic conductivity, good
Structural stability and ability preferably to oxygen catalysis reduction, the cathode material for becoming research the most extensive and using.However,
High temperature SOFC has many unfavorable factors, such as unstability of high preparation cost, operation and maintenance and greater probability, so that
IT-SOFC becomes research and development emphasis in recent years.Due to oxygen ionic conductivity of the LSM in 600-800 DEG C of temperature range compared with
It is low, greatly suppress its application in IT-SOFC.Conventional method is extended by mixing LSM and YSZ plasma conduction
TPB needed for oxygen catalysis reduction, and then it is promoted under mesophilic condition to the catalytic reduction activity of oxygen.However, mechanical mixture
LSM-YSZ composite cathode, its particle scale is generally micron level after the sintering, and the increase of TPB is also limited, in 750 DEG C of sun
Pole supports the also only about 200mW cm of the peak power density under plate SOFC-2.Research shows that by into porous electrode skeleton
The active site of ORR reaction can be dramatically increased by introducing nanoparticle catalyst by solution dipping method, and then promote cathode to oxygen
It is catalyzed the chemical property of reduction.
In research before, discovery introduces PdO into the LSM-YSZ cathode that tradition machinery mixes by solution dipping method
Nanoparticle catalyst can be such that its chemical property is obviously improved more than 7 times, this, which mainly has benefited from PdO particle, to significantly increase
Absorption and dissociation process of the LSM-YSZ cathode to oxygen, and then accelerate the progress of ORR reaction.However, in medium temperature electric discharge work item
Under part, PdO nano particle is easily reunited, grows up and tiles phenomenon, when so that the chemical property after being promoted is with electric discharge
Between linearly decay.Choose ZrO2As stabilizer, by PdO and ZrO2It is impregnated into LSM-YSZ cathode jointly, so that biggish
PdO particle is by tiny ZrO2Particle is surrounded.By characterizing PdO/ZrO2+ LSM-YSZ cathode 400,800 and
1200mAcm-2Chemical property and long-time stability under polarized current density test, and observe the SEM under the different polarization times
Shape appearance figure successfully inhibits grow up phenomenon of PdO nano particle under the conditions of high temperature discharge, so that PdO/ZrO2+
Chemical property and microstructural stability of the LSM-YSZ cathode under long-term discharging condition are significantly improved.
PdO/ZrO is prepared in the present invention2The plate monocell of Ni-YSZ anode-supported of+LSM-YSZ cathode, and study
Monocell chemical property and long-time stability.And it is calculated by DRT and is surveyed with CNLS fitting research monocell in long-term electric discharge
The variation of the RDS step of electrode reaction and its contacting between chemical property decaying during examination.
Cathode phase composition and its Oxygen Adsorption/dissociation capability characterization
Fig. 5 show PdO/ZrO2XRD spectrum of+LSM-YSZ the composite cathode in room temperature.Know that cathode mainly includes LSM
And YSZ phase and a small amount of PdO phase.Because of YSZ and ZrO2Crystal structure is identical, and ZrO2Content is too low, leads to its XRD diffraction
There are certain to be overlapped with YSZ phase peak position at peak, and is not easy to observe.Specific PdO and ZrO2The visible chapter 4 section of phase XRD result.
Fig. 6 show PdO/ZrO2, LSM-YSZ and PdO/ZrO2The O of three kinds of powders of+LSM-YSZ2- TPD curve.It is bent in figure
The waveform that line occurs in low-temperature zone be mainly due to the limited controlled temperature conditions of TPD device and gas flow rate independently built not
Caused by stablizing.For LSM-YSZ powder, TPD curve shows that there are two apparent oxygen desorption peaks.Start at 230 DEG C
Now and reach maximum desorption peaks at 420 DEG C and be referred to as α-oxygen peak, is mainly derived from the oxygen of LSM-YSZ chemical absorption of surface
Gas.Another reaches maximum desorption peaks at 795 DEG C and is then referred to as β-oxygen peak, mainly because of Mn in LSM lattice4+It is reduced to
Mn3+And the oxygen to escape in lattice.For PdO/ZrO2It is then by powder table positioned at 381 DEG C of desorption peaks for powder
Caused by the chemically adsorbing oxygen (α-oxygen peak) in face.It positioned at 753 DEG C of main peaks is decomposed in pure argon environment due to PdO
The oxygen discharged by metal Pd.About 803 DEG C of the aerial decomposition temperature of PdO, with the reduction of partial pressure of oxygen, decomposition temperature
Also it can reduce.For PdO/ZrO2For+LSM-YSZ powder, TPD curve is containing there are three peaks related with oxygen content.
According to above-mentioned LSM-YSZ and PdO/ZrO2Known to powder TPD Dependence Results: occurring at 130 DEG C, and reach highest at 320 DEG C and contain
The desorption peaks of amount are α-oxygen peak, this peak should be LSM-YSZ and PdO/ZrO2Produced by the chemisorption oxygen evolution of both powder.Phase
About 100 DEG C, and its are reduced than the temperature occurred in α-oxygen peak of LSM-YSZ, the peak and the temperature for reaching highest content
The oxygen content of release is also more, has absolutely proved PdO/ZrO2Addition increase LSM-YSZ to the active site of Oxygen Adsorption
With specific surface area so that it has absorption of the lower energy barrier to oxygen than traditional LSM-YSZ powder to the adsorption and diffusion of oxygen
Ability is also stronger.
PdO/ZrO2The microscopic appearance and chemical property of+LSM-YSZ cathode monocell
Fig. 7 show (a) PdO/ZrO2+ LSM-YSZ composite cathode monocell sectional view and (b) PdO/ZrO2+LSM-YSZ
Cathode shape appearance figure.As seen from the figure, monocell cathode layer, Ni-YSZ anode functional layer and the contact of YSZ electrolyte layer are good, thickness point
It Yue Wei not be about 20,10 and 10 μm.The PdO/ZrO of co-impregnation2Particle is evenly distributed on LSM-YSZ stephanoporate framework. ZrO2?
Grain is excessively tiny, the predominantly PdO particle that can be observed in SEM figure, average particle size particle size about 34nm.
Fig. 8 show PdO/ZrO2+ LSM-YSZ composite cathode monocell is at 650-750 DEG C with H2For fuel gas, air is
(a) I-V-P performance curve under oxidant and (b) its corresponding EIS figure.In order to avoid excessively high test temperature leads to PdO
Grain is decomposed, therefore chemical property highest test temperature is 750 DEG C in this experiment.By Fig. 8 a it is found that monocell is at 750 DEG C
Open-circuit voltage be 1.13V, illustrate battery assembly test leakproofness it is good.PdO/ZrO2+ LSM-YSZ cathode monocell exists
650, the peak power density at 700 and 750 DEG C is respectively 438,832 and 1207mW cm-2, it is significantly higher than traditional LSM-YSZ
Peak power density (~200mW cm of the cathode monocell at 750 DEG C-2), but slightly below PdO+LSM-YSZ cathode monocell
Peak power density (~1420mW cm at 750 DEG C-2), illustrate that PdO catalyst can be obviously improved LSM-YSZ cathode pair
The catalytic activity of ORR, and ZrO2Addition as stabilizer does not reduce its chemical property not significantly. PdO/ZrO2+LSM-
Peak power density at 700 DEG C of YSZ cathode monocell is 832mW cm-2, or even than synthermal lower LSCF cathode monocell
(~549mW cm-2) and LSM cladding LSCF cathode monocell peak power density (~655mW cm-2) also high[59], explanation
PdO/ZrO2+ LSM-YSZ cathode has a good application prospect in IT-SOFC.Fig. 8 (b) b is it is found that PdO/ZrO out2+LSM-
R of the YSZ cathode monocell at 650,700 and 750 DEG COValue is respectively 0.46,0.28 and 0.19 Ω cm2, illustrate battery component
Between contact it is good.Corresponding RPValue is respectively 1.04,0.75 and 0.354 Ω cm2, it is much smaller than tradition LSM-YSZ cathode monocell
R at 750 DEG CPIt is worth (~3.25 and 3 Ω cm2), also illustrate raising and the R of power densityPDipping is attributed to the fact that in the reduction of value
PdO particle increase LSM-YSZ cathode ORR reaction TPBs.
In order to probe into PdO/ZrO2The long-term discharge stability of+LSM-YSZ cathode monocell, experiment to it at 750 DEG C and
400mA cm-2235h is tested under discharge current density, output voltage is as shown in Figure 9 with the variation relation of discharge time.Single electricity
Pond is in 400mA cm-2Initial output voltage under discharge current density is 0.951V, slowly increases to 0.962V (16h) later,
This is primarily due to discharge current and makes electrochemical cathode performance improvement to the activation of LSM.Due to being tested in full battery I-V
Middle to apply instantaneous larger current, this portion of electrical current can also have an impact the length of LSM activation time.Later, defeated
Voltage slowly reduced with discharge time out, and reached stationary value 0.89V in 170h, illustrated PdO/ZrO2+LSM-YSZ
Cathode monocell chemical property reaches stable state.In research before, it has been shown that PdO+LSM-YSZ cathode monocell exists
700mA cm-2Output voltage under discharge current density is linearly decayed with discharge time, there is no performance still after testing 282h
Reach stable state；And the long greatly tunic of PdO particle agglomeration after discharge test, it is laid on LSM-YSZ skeleton.This explanation
PdO/ZrO in this experiment2+ LSM-YSZ cathode monocell stable electrochemical property is obviously improved, and is mainly due to
ZrO2The addition of stabilizer inhibits growing up for PdO particle.
Figure 10 show PdO/ZrO2+ LSM-YSZ cathode monocell is at 750 DEG C and 400mAcm-2Under long-term discharge test not
The data of EIS figure and the fitting of CNLS method under same time: (a) 0h, (b) 100h, (c) 170h and (d) 235h.In order to more main
Electrode polarization impedance RPIt is worth the variation relation with discharge time, when analyzing EIS figure by the R in figureO(mainly by single electricity
Caused by pond YSZ electrolyte and interface contact resistance) remove.In order to confirm PdO/ZrO2+ LSM-YSZ cathode monocell is in length
Voltage attenuation in phase discharge process be grown up by PdO particle agglomeration caused by, by using DRT (G (τ)) analysis method come
Confirm contribution of each electrode electro Chemical reaction step to overall polarization impedance Z (ω) and monocell performance.Polarization impedance Z (ω)
Relationship between G (τ) can be provided by formula (7):
It is the pole of Z (ω) real part when angular frequency tends to be infinite for the relaxation time of electrode reaction step, Z'(∞) in formula
Limit value.The visible pertinent literature of content more in terms of DRT theoretical calculation and related application.
(a) corresponding DRT curve is schemed according to the EIS in electric discharge periods different in Figure 10 and (b) DRT calculated result is opposite accidentally
Difference is as shown in figure 11.It can be seen that including 6 apparent peaks in every DRT curve, illustrate PdO/ZrO2+LSM-
YSZ cathode monocell includes 6 electrode electro Chemical reaction steps: P in long-term discharge test process1C、P2C、 P3CAnd P4CGeneration respectively
Epoxy ion from TPBs mass transfer to YSZ electrolyte process, oxygen molecule and oxygen atom at TPBs electronic processes, Oxygen Adsorption
TPBs process is diffused to dissociation process and oxygen molecule and oxygen atom；P1AWith P2AThen respectively represent the mass transport process hydrogen of proton
Diffusion process in porous anode layer.The highest peak DRT indicates that the corresponding electrode electro Chemical step exists most in Figure 11 (a)
Long relaxation time, usual corresponding electrode reaction are considered as the RDS step of entire ORR reaction.It is found that in discharge test
Before, P3CThe corresponding relaxation time longest of process shows that the absorption dissociation process of oxygen is the RDS step of ORR reaction, and with
The progress of discharge time, P1CThe relaxation time of process dramatically increases, this illustrates that RDS step becomes high frequency reaction zone oxonium ion and exists
Mass transport process in cathode.The relative error magnitudes of DRT calculated result can be obtained by formula (8):
Z " in formulameansFor the polarization impedance imaginary values of measurement, Z "fitFor the polarization impedance imaginary values of digital simulation, | Z (ω)
| it is the modulus of polarization impedance value.From Figure 11 (b) it is found that all DRT curve relative error magnitudes are respectively less than 1%, illustrate this experiment
The confidence level of middle DRT calculated result is high.Only when frequency values are more than 10KHz, relative error magnitudes are slightly larger, this should be high frequency region
Caused by inductive effect, and its relative error magnitudes is still less than 1%.
In order to preferably study PdO/ZrO2+ LSM-YSZ cathode monocell in long-term discharge test RDS step with putting
The variation of electric time and the basic reaction step of each electrochemistry are to RPThe contribution of value, this experimental construction contain capacitor and resistance member
The active balance circuit of part is come absorption, dissociation involved in the EIS map that is fitted in test process and electrochemical reaction process, in detail
Thin fitting result is as shown in table 1.In the balance equivalent circuit, ROFor total ohmage value, CPE2CWith CPE2AFor Chang Xiangwei
Angle element, R1C, R2C, R3CAnd R4CRespectively correspond four reaction step P of cathode1C、P2C、P3CAnd P4CPolarization impedance value, R1AWith
R2ARespectively correspond two reaction step P of anode1AWith P2APolarization impedance value, detailed CNLS fitting result is as shown in figure 12.
Figure 13 show PdO/ZrO2+ LSM-YSZ cathode is at 750 DEG C and 400mAcm-2R under testPIt is worth and fits
Polarization impedance value corresponding to six electrode reaction steps changes with time relationship.It is found that at 750 DEG C and 400mAcm-2Test
Under 235h, PdO/ZrO2The R of+LSM-YSZ cathodePIt is worth from 0.354 initial Ω cm2It increases separately to 0.574 Ω cm2
(100h)、0.67Ωcm2(170h) and 0.685 Ω cm2(235h)；And RPValue is only 170 to the growth rate between 235h
0.023%h-1。RPValue is kissed with the output voltage in the variation tendency and Fig. 9 of discharge time with the variation tendency of discharge time substantially
It closes, illustrates PdO/ZrO2The chemical property decaying of+LSM-YSZ cathode monocell in long-term discharge test is the pole by electrode
Change caused by impedance value increase.In Figure 11, it can be found that in addition to R3CAs discharge time reduces, other polarization impedance values are equal
Increase；And R1CIt significantly increases, becomes entire RPThe main contributions source of value illustrates its corresponding oxonium ion in TPBs
The process of place mass transfer to YSZ electrolyte is suppressed, and is the RDS step of entire electrode reaction.It is therefore contemplated that output voltage
Decaying be and R1CIncrease it is closely related.
Figure 14 show PdO/ZrO2+ LSM-YSZ cathode monocell is in 750 DEG C and 400mAcm-2Under different discharge times
The corresponding Bode figure of EIS figure and the data of CNLS fitting: (a) 0h；(b)100h；(c)170h；(d)235h.It is found that initial
Corresponding 6 peak frequency values are respectively 1584.9,316.23,63.09,12.59,2.51 and 0.63Hz in the Bode figure of 0h；When
When being discharged to 100h, the corresponding frequency values of 6 electrode reactions move to right increase to 3981.07 respectively, 630.96,125.89,
25.12,7.94 and 0.794Hz；When continuing to be discharged to 170h, corresponding frequency values are respectively 3981.07,630.96,
125.89,25.12,7.94 and 0.794Hz；And after being finally discharged to 235h, corresponding frequency values are respectively 3981.07,
794.32,158.48,39.81,7.94 and 0.794Hz.When frequency values corresponding to each electrode reaction are with electric discharge in the Bode figure
Between variation relation it is consistent with DRT result, also demonstrate PdO/ZrO2+ LSM-YSZ cathode monocell is in long-term discharge process
In, electrode reaction RDS step from the Oxygen Adsorption dissociation process of low frequency reaction zone be changed into the oxonium ion of high frequency reaction zone from
TPBs mass transfer to YSZ electrolyte process.
PdO/ZrO2+ LSM-YSZ cathode microscopic appearance with discharge time variation
Figure 15 show PdO/ZrO2+ LSM-YSZ cathode monocell is in 750 DEG C of and400mAcm-2Under different discharge times
SEM figure: (a) 100h, (b) 170h, (c) 235h and (d) PdO average particle size particle size with discharge time variation relation.From figure
7 it is found that PdO average particle size particle size about 34nm.In high temperature and discharge test 100h, PdO average particle size particle size increases to 45nm；
Continue to be discharged to 170 and 235h, average particle size particle size increases to 49nm and significant change no longer occurs, illustrates in subsequent 65h
In discharge process, the reunion of PdO particle grows up phenomenon by ZrO tiny around it2Particle successfully inhibits, and then keeps good
Good stable electrochemistry output performance.In chapter 4 section, PdO/ZrO is had studied2+ LSM-YSZ cathode is in not same polarization
Rule of growing up under current density finds that it follows one from limit relaxation dynamic growth process (formula 5).Pass through comparison diagram 15
(d) rule of growing up of PdO particle in finds that it is still suitable for this from the long large-sized model of limit relaxation dynamic, therefore further utilizing should
PdO average particle size particle size data in models fitting Figure 15 (d), obtain its relaxation time about 65.2h.Meanwhile also demonstrating PdO
The TPBs length that particle growth will lead to ORR reaction reduces, and oxonium ion is mainly inhibited to be transmitted to YSZ electrolyte from TPBs
Process, lead to performance degradation.And then this is used to be fitted R from limit relaxation dynamic modelP、R1CAnd output voltage V with electric discharge when
Between the data that change, fitting result as shown in Figure 13 and Fig. 9, show that its corresponding relaxation time is respectively 65.5,66.8 respectively
And 66.1h.This is very close with the relaxation time of PdO particle growth process, illustrates that growing up for PdO particle results in RPWith R1C
The increase of value, and then cause the reduction of output voltage values.
PdO/ZrO2The introducing of beaded catalyst increases absorption and dissociation capability of the LSM-YSZ cathode to oxygen, that is, subtracts
Small R3CWith R4CValue；The active site and TPB length for increasing ORR reaction simultaneously, that is, reduce R1CWith R2CValue.Therefore, from
And make PdO/ZrO2The overall polarization impedance R of+LSM-YSZ cathode monocellPValue reduces and chemical property is obviously improved.
During long-term discharge test, as the reunion of PdO particle is grown up, specific grain surface is long-pending and connects with LSM-YSZ skeleton
The TPB length of touching is reduced, so as to cause R1C、R2C、R3CAnd R4CIncrease.However, as caused by the product reduction of PdO specific grain surface
The influence that slows down of Oxygen Adsorption dissociation is offset by LSM activation, therefore R3CIt maintains to stablize after LSM activation, and
R4CIt represents oxygen atom and diffuses to the impedance value of process at TPBs and then slightly increase.Oxonium ion closely related with TPB length simultaneously
Impedance value R corresponding to mass transport process1CThen significantly increase (such as Figure 13 and table 1).In the discharge process of 235h, Ni-YSZ sun
Pole is as research and the anode material that is most widely used, and significant change can't occur for structure, therefore R2AHydrogen is represented more
Significant change will not occur for the impedance value of the diffusion process in the anode of hole.And since oxonium ion is transmitted to the mistake of YSZ from TPBs
Journey is obstructed, prevent ORR generates oxonium ion from timely reacting with proton, is caused proton in anode excessive concentration, is inhibited
Its transmission process, so that R1AValue increases.As PdO particle is no longer grown up, pole corresponding to all electrode reaction steps
Change impedance value and reach stable state, illustrates PdO/ZrO2+ LSM-YSZ cathode has preferable application in IT-SOFC.
The present invention utilizes solution co-impregnation by PdO and ZrO2It is introduced into LSM-YSZ cathode monocell, prepares PdO/
ZrO2The plate monocell of+LSM-YSZ/YSZ/Ni+YSZ anode-supported.By with H2It is that oxic gas carrys out table for fuel gas, air
Its initial chemical property at 650 to 750 DEG C is levied, and to it at 750 DEG C and 400mAcm-2Discharge current density under into
Row is up to the stability test of 235h, can obtain and such as draw a conclusion:
1) co-impregnation PdO/ZrO2Its potential barrier to Oxygen Adsorption can be reduced into LSM-YSZ cathode porous skeleton, increased
Its absorption dissociation capability to oxygen, the progress that ORR can be accelerated to react.
2)PdO/ZrO2Peak power density of+LSM-YSZ cathode the monocell at 650 to 750 DEG C is respectively 438,832
And 1207mW cm-2, it is significantly higher than traditional LSM-YSZ cathode monocell performance, the LSCF of even higher than pure LSCF and LSM cladding
Cathode monocell chemical property.PdO/ZrO2+ LSM-YSZ cathode monocell is at 750 DEG C and 400mAcm-2Discharge current it is close
It is carried out under degree after the stability test of 170h, output voltage stabilization is in 0.89V.It is defeated in subsequent 65h discharge test
Voltage is held essentially constant out.
3)PdO/ZrO2A kind of limit relaxation dynamic process certainly is presented in PdO particle growth in+LSM-YSZ cathode, utilizes this
Its average particle size particle size, polarization impedance value and output voltage data are fitted from limit relaxation dynamic model, find three's relaxation time
Closely, also demonstrating the increase of monocell polarization impedance value and output voltage decaying is as caused by PdO particle growth.
4) PdO particle growth results in the reduction of TPB length, mainly inhibits the oxonium ion mass transport process in ORR reaction,
Cause whole ORR reaction rate to be obstructed, leads to monocell performance degradation.As PdO particle is no longer grown up, each reaction step of electrode
Reach stable state, at this point, monocell output performance also reaches stable.
The above is a preferred embodiment of the present invention, cannot limit the right model of the present invention with this certainly
It encloses, it is noted that for those skilled in the art, without departing from the principle of the present invention, may be used also
To make several improvement and variation, these, which improve and change, is also considered as protection scope of the present invention.
Claims (10)
1. a kind of large-area flat-plate type solid oxide fuel cell palladium oxide composite cathode preparation method, which is characterized in that packet
Include following steps:
Palladium oxide and its stabilizer are injected on the cathode of previously prepared large-area flat-plate type solid oxide fuel cell
Nano particle, and carry out sinter molding.
2. large-area flat-plate type solid oxide fuel cell palladium oxide composite cathode preparation side according to claim 1
Method, it is characterised in that:
The stabilizer is zirconium base stabilizer.
3. large-area flat-plate type solid oxide fuel cell palladium oxide composite cathode preparation side according to claim 2
Method, it is characterised in that:
The zirconium base stabilizer is YSZ or zirconium oxide.
4. large-area flat-plate type solid oxide fuel cell palladium oxide composite cathode preparation side according to claim 3
Method, which is characterized in that
The nano particle of palladium oxide and its stabilizer is injected in the cathode of the large-area flat-plate type solid oxide fuel cell
Concrete mode be,
The mixed solution containing palladium oxide and its stabilizer is prepared, and by the mixed solution to the large-area flat-plate type solid oxygen
The cathode of compound fuel cell is sprayed.
5. large-area flat-plate type solid oxide fuel cell palladium oxide composite cathode preparation side according to claim 4
Method, it is characterised in that:
Spraying is carried out to the cathode of the large-area flat-plate type solid oxide fuel cell to specifically include,
After the mixed solution is atomized, the mixed solution after atomization is sprayed by the large area by spraying equipment and is put down
The surface of template solid oxide fuel cell palladium oxide composite cathode；
The sinter molding specifically includes,
The large-area flat-plate type solid oxide fuel cell palladium oxide composite cathode is dried and is heat-treated, described
The nano-catalytic with nanostructure is formed in large-area flat-plate type solid oxide fuel cell palladium oxide composite cathode skeleton
Oxidant layer.
6. large-area flat-plate type solid oxide fuel cell palladium oxide composite cathode preparation according to claim 4 or 5
Method, it is characterised in that:
The mixed solution of the preparation containing palladium oxide and its stabilizer, specifically includes,
By PdCl2With Zr (NO3)4·5H2O or with Zr (NO3)4·5H2O and yttrium salt mixing, are added hydrochloric acid, are sufficiently stirred, formed
Mixing salt solution；
Citric acid is added into the mixing salt solution and is added EDTA's as the first complexing agent, then in the mixing salt solution
Ammonia spirit is as the second complexing agent；
It adds ammonia spirit to the mixing salt solution pH value and rises to 7.8~8.2；By the mixing salt solution carry out oil bath,
Stirring, evaporation water add surfactant.
7. large-area flat-plate type solid oxide fuel cell palladium oxide composite cathode preparation side according to claim 6
Method, it is characterised in that:
The stabilizer is zirconium oxide；
It is described by PdCl2With Zr (NO3)4·5H2O or with Zr (NO3)4·5H2O and yttrium salt mixing are specifically, by PdCl2With Zr
(NO3)4·5H2O mixing；
The PdCl2With Zr (NO3)4·5H2The molar ratio of O is 95:5~80:20)；For to the large-area flat-plate type solid
In the mixed solution that the cathode of oxide fuel cell is sprayed, the concentration of palladium oxide is 0.20~0.50mol/L, zirconium oxide
Concentration be 0.05~0.15mol/L.
8. large-area flat-plate type solid oxide fuel cell palladium oxide composite cathode preparation side according to claim 6
Method, it is characterised in that:
The surfactant is alcohols activating agent.
9. large-area flat-plate type solid oxide fuel cell palladium oxide composite cathode preparation side according to claim 6
Method, it is characterised in that:
The surfactant is isopropanol.
10. a kind of compound by the described in any item large-area flat-plate type solid oxide fuel cell palladium oxides of claim 1-9
The large-area flat-plate type solid oxide fuel cell palladium oxide composite cathode that cathode preparation method is prepared, feature exist
In:
The nanoparticle size of the palladium oxide and its stabilizer is not more than 30nm.
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