CN107555489B - A kind of A cathode material for solid-oxide fuel cell, preparation method and application more than needed - Google Patents
A kind of A cathode material for solid-oxide fuel cell, preparation method and application more than needed Download PDFInfo
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Abstract
The present invention relates to a kind of A Pr cathode material for solid-oxide fuel cell having more than needed and preparation method thereof, cathode material ingredient formula is Pr1+xBaCo2O6‑δ, wherein x indicates that Pr surplus capacity, 0≤x≤0.1, δ indicate Lacking oxygen content, belong to cathode material for solid-oxide fuel cell technical field.By in perovskite material PrBaCo2O6‑δMiddle A Pr is more than needed and improves PrBaCo2O6‑δChemical property.Pr A Pr more than needed1+xBaCo2O6‑δMaterial all increases in conductivity, oxygen diffusion and oxygen exchange capacity, and the polarization impedance at 600 DEG C is only 0.046 Ω cm2, peak power output of the corresponding monocell at 650 DEG C be up to 1503 mWcm‑2.PrBaCo can be significantly reduced in the present invention2O6‑δThe polarization impedance of cathode, so that the industrial applications to intermediate temperature solid oxide fuel cell contribute.
Description
Technical field
The present invention relates to a kind of cathode material for solid-oxide fuel cell and its preparation method and application, and in particular to arrives
Cathode material for solid-oxide fuel cell Pr A Pr more than needed1+xBaCo2O6-δAnd its preparation method and application.
Background technique
Solid oxide fuel cell is a kind of new energy conversion equipment that chemical energy can be directly changed into electric energy,
Because it has many advantages, such as energy conversion efficiency height, cleanliness without any pollution, fuel diversification, structure of whole solid state and does not use noble metal,
It is a kind of efficient alternative energy source for realizing energy-saving and emission-reduction and sustainable development.The work temperature of traditional solid oxide fuel cell
Degree is 800~1000 DEG C, and high-temperature operation condition limits the exploitation of the stability of solid oxide fuel cell, cost etc., sternly
The development of its large-scale commercial is hindered again.Such as the generation that cathode is reacted with electrolyte interface under the high temperature conditions；Electrolyte, electricity
The difference of pole and sealing material thermal expansivity leads to the reduction of battery structure stability and the high cost of heat-resisting material etc. all
It is the obstruction condition of large-scale commercial.In order to improve the stability of fuel cell and reduce material cost, middle low temperature (400
~800 DEG C) operating temperature be its development trend.But after dropping to middle low temperature with operating temperature, polarization of electrode impedance
Especially cathodic polarization impedance sharply becomes larger, and chemical property is caused to reduce, therefore needs the cathode material of exploitation high electrical performance
For intermediate temperature solid oxide fuel cell.
Summary of the invention
The object of the present invention is to provide the cathode material for solid-oxide fuel cell Pr that a kind of perovskite A Pr have more than needed1+ xBaCo2O6-δAnd its preparation method and application, to improve existing cathode material in the deficiency of middle cryogenic property.PrBaCo2O6-δBase A
After position Pr is more than needed, conductivity, diffusion coefficient, oxygen exchange coefficient, chemical property of cathode material etc. can be improved, so that negative
Pole material Pr1+xBaCo2O6-δIt can be applied in low-temperature working.
The first aspect of the invention provides:
A kind of cathode material for solid-oxide fuel cell, composition general formula are AA ' B2O6-δ, molecular formula are as follows: Pr1+ xBaCo2O6-δ, wherein x represents the surplus capacity of Pr, and δ is Lacking oxygen content.
X value range is 0.01~0.1, more preferably 0.05.
The second aspect of the invention provides:
The preparation method of above-mentioned cathode material for solid-oxide fuel cell is by Pr (NO3)3·6H2O, Ba (NO3)2
With Co (NO3)2·6H2O is prepared by the stoichiometric ratio in molecular formula by sol-gal process.
The preparation method, step are:
By Pr (NO3)3·6H2O、Ba(NO3)2With Co (NO3)2·6H2O is stoichiometrically added into deionized water, adds
Heat simultaneously stirs evenly；
Ethylenediamine tetra-acetic acid and citric acid are added, the pH that ammonium hydroxide is added dropwise to solution later is to stir between 6~7 in heating
Moisture evaporation is set to obtain spawn under conditions of mixing；
Spawn is placed in baking oven and is dried, obtains the presoma of cell cathode, then by presoma in Muffle
It is calcined in furnace, obtains required battery cathode material.
The molar ratio of the integral molar quantity of ethylenediamine tetra-acetic acid and citric acid and Pr, Ba, Co is 2:1:1.
The condition of the drying course is 150~250 DEG C of 2~8 h of processing.
The condition of the calcination process is 950~1150 DEG C of 3~10 h of calcining.
The third aspect of the invention provides:
Application of the above-mentioned cathode material in solid oxide fuel cell.
The application, the anode material in solid oxide fuel cell is the mass ratio of NiO and SDC or YSZ by 6:4
The composite anode of formation.
The application, the electrolyte in solid oxide fuel cell is SDC.
The fourth aspect of the invention provides:
Pr more than needed is for reducing Pr1+xBaCo2O6-δApplication in structure of double perovskite cell parameter.
Pr more than needed is for improving Pr1+xBaCo2O6-δApplication in cathode material conductivity.
Pr more than needed is for improving Pr1+xBaCo2O6-δApplication in cathode material oxygen transmission performance.
Pr more than needed is for improving Pr1+xBaCo2O6-δApplication in cathode material oxygen switching performance.
Pr more than needed is for reducing Pr1+xBaCo2O6-δApplication in cathode material oxygen desorption temperature.
Pr more than needed is for increasing Pr1+xBaCo2O6-δApplication in cathode material in the valence state of Co element.
Pr more than needed is for increasing Pr1+xBaCo2O6-δCo in cathode material4+Application in concentration.
Pr more than needed is for reducing Pr1+xBaCo2O6-δThe application of cathode material thermal expansion coefficient.
Pr more than needed is for reducing Pr1+xBaCo2O6-δApplication in cathode material impedance.
Pr more than needed is for reducing Pr1+xBaCo2O6-δApplication in cathode material activation energy.
Pr more than needed is using Pr for improving1+xBaCo2O6-δAnswering in the fuel cell output power of cathode material
With.
Beneficial effect
It is adulterated using EDTA-CA and obtains A cation Pr Pr more than needed1.05BaCo2O6-δ(PBC-105) it is used as low in novel
Temperature solid-oxide fuel battery cathode material.By to PrBaCo2O6-δ(PBC) and after PBC-105 progress XRD refine it finds,
Pr more than needed is instead of the position Ba for being all A, so that its cell parameter reduces.Conductance of this experiment also to PBC and PBC-105
Rate, conductance relaxation (ECR), thermogravimetric-mass spectrum (TG-MS), XPS fitting, thermal expansion coefficient (TEC) etc. have carried out systematic research.
EIS test carried out to PBC and PBC-105 in air atmosphere, test result show PBC-105 600 DEG C impedance by
The 0.081 Ω cm of PBC2Become 0.046 Ω cm2, reduce by about one time.Pass through the prolonged impedance of 200 h at 600 DEG C
It is found after stability test, impedance does not increase.The monocell prepared using Ni-SDC as anode-supported is at 650 DEG C, 600 DEG C, 550
DEG C, 500 DEG C, 450 DEG C of output power respectively reaches 1.50 W cm-2, 1.1 W cm-2, 0.73W cm-2,0.41 W cm-2, 021 W cm-2.PBC-105 can significantly improve its chemical property compared with PBC, have under middle low temperature higher defeated
Power and good stability out are suitable as middle low-temperature solid oxide battery cathode material.
Detailed description of the invention
Fig. 1 is the XRD spectrum at room temperature of PBC-095, PBC, PBC-105 and PBC-110, and wherein the region a is 20~90 ° of models
The XRD spectrum of interior test is enclosed, the region b is the XRD spectrum tested within the scope of 39.5~41 °；
Fig. 2 is PBC, and PBC-105 calcines the XRD spectrum after 2 h at 900 DEG C after mixing with SDC respectively；
Fig. 3 is that PBC and PBC-105 are tested after the calcining of the long-time of 50 h at 1100 DEG C in air atmosphere
XRD spectrum；
Fig. 4 is high temperature XRD test (HT-XRD) spectrogram of PBC-105；Wherein the region a and the region b be respectively 10~90 ° and
Spectrogram is tested within the scope of 31~34 °；
Fig. 5 is the refine XRD spectrum of PBC；
Fig. 6 is the refine XRD spectrum of PBC-105；
Fig. 7 be PBC series powder in air atmosphere in 300~DEG C 850 DEG C within the scope of the conductivity tested every 25 DEG C
Figure；
Fig. 8 is that PBC and the PBC-105 partial pressure of oxygen at 650 DEG C are schemed by 0.1 atm mutation to the ECR after 0.2 atm.
Fig. 9 is the D that PBC and PBC-105 are calculated within the scope of 500~750 DEG C by ECR test valuechemChanging rule；
Figure 10 is the K that PBC and PBC-105 are calculated within the scope of 500~750 DEG C by ECR test valuechemVariation rule
Rule；
Figure 11 is thermogravimetric (TG) test curve that PBC series powder carries out in a nitrogen atmosphere；
Figure 12 is thermogravimetric (TG) test curve that PBC series powder carries out in air atmosphere；
Figure 13 is the oxygen signal test that PBC series powder carries out in a nitrogen atmosphere；
Figure 14 is the XPS fitting result of Pr and Co element in PBC；
Figure 15 is the XPS fitting result of Pr and Co element in PBC-105；
Figure 16 is PBC and PBC-105 the TEC test curve within the scope of 200~1000 DEG C；
Figure 17 is the EIS test result that PBC series cathode is carried out at 600 DEG C；
Figure 18 is the activation energy that PBC series cathode is calculated according to the EIS result tested within the scope of 550~750 DEG C
Curve；
The Symmetrical cells that Figure 19 is PBC-105 to be prepared using SDC as electrolyte are at 600 DEG C with 60 ml min-1Air stream
The impedance stability figure of 200 h of the lower test of speed；
Figure 20 is the I-V-P that PBC is carried out within the scope of 500~750 DEG C using Ni-YSZ as monocell prepared by anode-supported
Test curve figure；
Figure 21 is the I- that PBC-105 is carried out within the scope of 500~750 DEG C using Ni-YSZ as monocell prepared by anode-supported
V-P test curve figure；
Figure 22 is the electrochemical impedance spectroscopy that PBC is tested in I-V-P test process；
Figure 23 is the electrochemical impedance spectroscopy that PBC-105 is tested in I-V-P test process；
Figure 24 be PBC-105 be cathode, Ni-SDC be anode-supported preparation monocell (Ni-SDC | | SDC | | PBC-
105) the I-V-P curve graph tested within the scope of 450~650 DEG C；
Figure 25 be PBC-105 be cathode, Ni-SDC be anode-supported preparation monocell (Ni-SDC | | SDC | | PBC-
105) electrochemical impedance spectroscopy tested in the I-V-P test process tested within the scope of 450~650 DEG C；
Figure 26 be the monocell that is prepared using PBC-105 as cathode at 550 DEG C with 600 mA cm-2Under conditions of carry out
The stability test of 50 h；
Figure 27 is with Ni-YSZ | | YSZ | | SDC | | section and cathode surface after the monocell test of PBC series preparation
SEM figure.Wherein the region a and the region b are Ni-YSZ respectively | | YSZ | | SDC | | section and yin after the monocell test of PBC preparation
The SEM of pole surface schemes；The region c and the region d are Ni-YSZ respectively | | YSZ | | SDC | | after the monocell test of PBC-105 preparation
The SEM of section and cathode surface figure.
Specific embodiment
Embodiment 1
The present embodiment provides a kind of above-mentioned intermediate temperature solid oxide fuel cell cathode material Pr1.05BaCo2O6-δSystem
Preparation Method, the specific steps are as follows: the cobalt nitrate for weighing the praseodymium nitrate of 5.7096 g, the barium nitrate of 3.2668 g, 7.2758 g adds
A small amount of deionized water dissolving.By ethylenediamine tetra-acetic acid: citric acid monohydrate: the molar ratio that total metal ion is 1:2:1 weighs 15g's
Ethylenediamine tetra-acetic acid, 21 g citric acid monohydrates are dissolved in deionized water as complexing agent.It is molten by being added dissolved with the solution of complexing agent
After having metal ion solution, suitable ammonium hydroxide is added dropwise, pH value of solution is caused to reach between 7, cause water is then stirred under conditions of magnetic agitation
Point evaporating completely obtains spawn.Spawn is placed in baking oven and obtains institute after 250 DEG C of 5 h of temperature lower calcination
The foam-like presoma needed.Presoma is placed in high temperature Muffle furnace and obtains required yin after 1100 DEG C of 5 h of temperature lower calcination
Pole powder.
Check experiment
It can be correspondingly prepared according to the preparation method in embodiment 1 by adjusting the additional amount of praseodymium nitrate
PrBaCo2O6-δ(PBC)、Pr0.95BaCo2O6-δ(PBC-095)、Pr1.10BaCo2O6-δ(PBC-110) cathode material.
The characterization of material
PBC series of samples crystal structure is by room temperature X-ray diffraction (XRD) with the progress of 0.02 ° of interval within the scope of 20-90 °
Test.The diffraction curve of acquisition is analyzed by general structure analysis system (GSAS) and EXPGUI interface.Sample specific surface
Long-pending and pore-size distribution passes through BELSORP | | device is based on N under the boiling temperature of liquid nitrogen2Absorption-desorption (BET) curve comes
It obtains.PBC presoma is tested in 50 ~ 1150 DEG C of progress thermogravimetric-mass spectrums (TG-MS), analysis PBC presoma is increased in temperature
During mass change and CO2Situation is desorbed.Tabletting after suitable PBC series cathode powder is mixed with KBr, at room temperature
450~4000 cm-1Range carries out Fourier transform infrared spectroscopy (FT-IR) test.After PBC series morphology microstructure and test
Monocell Cross Section Morphology scanning electron microscope (SEM) photograph is obtained at 200 KV by G2 T20 testing electronic microscope.
The preparation of Symmetrical cells and monocell
Symmetrical cells use electrode | | SDC | | electrode structure is tested for EIS.SDC powder is 200
After being pressed into the disk of 15 mm of diameter under MPa pressure, 5 h of high-temperature calcination obtains testing institute for Symmetrical cells at 1350 DEG C
The electrolyte sheet needed.Porous PBC series cathode is prepared using spray coating method, and a certain amount of cathode powder is dissolved in suitable isopropyl
In the mixed solution of alcohol, ethylene glycol and glycerine, ensure that cathode is uniformly dispersed with the help of high energy ball mill.It will be resulting
PBC cathode slurry uniformly sprays under the promotion of inert gas on the both sides electrolyte SDC.Symmetrical cells after preparation are in sky
In 900 DEG C of 2 h of calcining under gas atmosphere.The tape casting and dry pressing preparation is respectively adopted in the monocell of anode-supported.The tape casting preparation
Monocell use Ni-YSZ | | YSZ | | SDC | | cathode structure, dry pressing preparation monocell use Ni-SDC | | SDC | |
Cathode structure, the effective cathode area of battery are 0.45 cm2。
Electro-chemical test
The Symmetrical cells electrode prepared | | SDC | | electrode uses Solartron 1287
Potentiostat/galvanostat and Solartron 1260A frequency response analyzer device is in sky
In 750 ~ 550 under gas atmosphereoEIS test is carried out within the scope of C.Under OCV situation with the stimulation voltage of 10 mV every 50 DEG C
750~550 oFrom 100 kHz test to 0.1 Hz in C temperature range.The monocell Ni-YSZ of anode-supported | | YSZ | | SDC | |
Cathode and Ni-SDC | | SDC | | cathode is using self-control fuel cell test respectively in 550 ~ 750 DEG C and 450 ~ 650 DEG C
Under tested.Hydrogen is in test with 80 mL min-1Flow velocity be passed through anode-side, cathode exposure is in air.In four probe moulds
I-V polarization curve is collected using digital source meter (Keithley 2420) under formula.
Characterization result
1.XRD characterization
Fig. 1 is the XRD spectrum at room temperature of PBC-095, PBC, PBC-105 and PBC-110, the wherein region a and the region b difference
For the XRD spectrum tested within the scope of 20~90 ° at room temperature and 39.5~41 °.It can be seen from the figure that three samples are all in
Reveal good double-perovskite phase.Show that the peak position PBC-105 and PBC-110 compared with PBC, deviates, this and Pr to wide-angle3+
(1.30) ionic radius ratio Ba2+(1.61) smaller to match.
Fig. 2 is PBC, and PBC-105 calcines the XRD spectrum after 2 h at 900 DEG C after mixing with SDC respectively.From figure
As can be seen that not occurring the peak in addition to PBC and SDC after high-temperature calcination, illustrating PBC and PBC-105 and SDC in height
Good compatibility can be kept under temperature, phase reaction will not be generated.Fig. 3 is for PBC and PBC-105 in 1100 in air atmosphere
The XRD spectrum tested after the calcining of the long-time of 50 h at DEG C, it can be seen from the figure that PBC and PBC-105 have at high temperature
There is good phase structure stability.
2.HT-XRD characterization
In order to probe into whether the phase structure of PBC-105 at high temperature can keep, high temperature XRD survey has been carried out to PBC-105
It tries (HT-XRD).The region a and the region b of Fig. 4 is respectively the XRD spectrum that PBC-105 is tested within the scope of 10~90 ° and 31~34 °
Figure.Test temperature section is to be tested from 300 DEG C every 100 DEG C to 750 DEG C the temperature rise period, and temperature-fall period is from 750 DEG C every 100 DEG C
It tests to 300 DEG C.Test result shows that PBC-105 maintains good double-perovskite peak at high temperature.With the liter of temperature
Height, peak position are deviated to low-angle, this is because thermal reduction reaction, Pr and Co element difference has occurred in high temperature PBC-105
By 4+With 3+It is transformed into 3+With 2+, cause ionic radius become larger and caused by.Opposite process then has occurred in temperature-fall period.
3. the Comparative result of refine XRD
In order to obtain further structural information, refine processing is carried out to PBC and PBC-105, Fig. 5 and Fig. 6 are respectively
The refine XRD spectrum of PBC and PBC-105.It can be seen from the figure that PBC and PBC-105 are P 4/mmm structures, wherein PBC,
Cell parameter a=b=3.90707 (8), c=7.6300 (1), unit cell volume are V=116.474 (7)3, Rp=3.93%,
Rwp=5.11%, χ2=2.028；PBC-105, cell parameter a=b=3.90109 (7), c=7.6300 (1), unit cell volume V
=116.194(7) Å3, Rp=4.11%, Rwp=5.32%, χ2=1.787.It can be seen that A structure of double perovskite structure cells more than needed
Parameter becomes smaller, this may be position of the Pr instead of Ba because the amount that Pr has more than needed exists not instead of in the form of PrOx.In essence
Repair and also find out A Pr and Ba in result there are some randomnesses (disorder), exactly because this may Pr cause instead of Ba
's.
4.ICP analysis
Table 1 is PBC-105 in the ion concentration test (ICP) carried out after pernitric acid dilution dissolution, in terms of test structure
Out, the concentration ratio Pr:Ba:Co of each metal ion is respectively 1.05:1.00:2.00 in PBC-105, this and theoretical value Pr:Ba:Co
1.05:1.00:2.00 it is very close, illustrate in PBC-105 have more than needed Pr be into lattice.
Each metallic element concentration ratio in 1 PBC-105 of table
5. conductivity is tested
Fig. 7 is for PBC series powder in the conductivity map tested within the scope of 300~850 DEG C every 25 DEG C in air atmosphere.
It can be seen from the figure that the conductivity of PBC-095, PBC, PBC-105 and PBC-110 are within the scope of 300~850 DEG C all with temperature
The increase of degree and reduce, show the characteristic similar with other cobalt-based perovskite materials: as the temperature rises, oxygen in lattice
Release and Co4+The reduction of ion concentration, so that conductivity reduces therewith.Wherein the Conductivity Ratio PBC of PBC-095 wants low.
The Conductivity Ratio PBC's of PBC-105 is higher, this may be the Pr substitution position Ba because more than needed.
6. conductance relaxation method (electrical conductivity relaxation, ECR) characterizes
Fig. 8 is that PBC and the PBC-105 partial pressure of oxygen at 650 DEG C are schemed by 0.1 atm mutation to the ECR after 0.21 atm.From
As can be seen that the stabilization time of PBC is in 2000 s or so in figure, and the stabilization time of PBC-105 only need to be less than 1000 s, explanation
Its oxygen transmittability can be significantly improved after Pr is more than needed in PBC.
Fig. 9 and Figure 10 is respectively PBC and PBC-105 500 ~ 750oThe D being calculated within the scope of C by ECR test valuechem
And KchemChanging rule.It can be seen from the figure that at 750 DEG C, the D of PBC-105chemIt is 6.47 × 10-5 cm2 s-1, PBC's
DchemIt is 2.64 × 10-5 cm2 s-1.With the decline of temperature, the D of PBC-105chemIt is bigger than the gap of PBC, especially in low temperature
At 500 DEG C, the D of PBC-105chemBigger than PBC nearly quantity ratio.Further comparison discovery, the K of PBC-105 and PBCchem
Value rule and DchemEqually, with the decline of temperature, the K of PBC-105chemIt is slower than PBC decline.Especially 500 DEG C of low temperature
When, the K of PBC-105chemNearly an order of magnitude is also increased than PBC.Its oxygen can significantly be improved by illustrating in PBC that Pr is more than needed
Diffusion and oxygen exchange capacity, and then its electrocatalysis characteristic can be improved.
7.TG-MS test
Figure 11 and Figure 12 is respectively the TG test that PBC series powder carries out under nitrogen and air atmosphere.Figure 13 is PBC system
The oxygen signal test that column powder carries out in a nitrogen atmosphere.From test result as can be seen that PBC four samples of series are all 300oThere is first peak in C or so, is all the phase one risen from high temperature test to 300 DEG C of conductivity when this is tested with conductivity
It causes.Wherein PBC-105 is compared with PBC, first peak occurs in lower temperature.And the low temperature alpha oxygen of PBC-105 is de-
Attached peak ratio PBC's is strong, because the initial desorption peaks of PBC-105 and maximum intensity peak position are to the left, can be desorbed at a lower temperature,
Illustrate that PBC-105 is easier to be desorbed, performance is more active.And the desorption peaks of high temperature beta oxygen are then weaker than PBC, reason should
It is caused by the Pr having more than needed in PBC-105 is entered in the lattice of PBC.
8.XPS analysis
Figure 14 and Figure 15 is respectively the XPS fitting result of Pr and Co element in PBC and PBC-105.It can be obvious from figure
Find out, PBC-105 and PBC first compare, Pr3+ 3d5/2:Pr4+3d5/2 is held essentially constant, and the Co of PBC-105 and PBC3+
2p3/2:Co4+The ratio of 2p3/2 becomes smaller, and illustrates that PBC-105 is compared with PBC, Co4+Concentration increases, and specific value is shown in Table
2.This is consistent with conductivity before and TG-MS test result, its Co can be improved after Pr is more than needed in PBC4+Concentration.In order to prove this
Phenomenon has carried out the non-titration of oxygen to PBC and PBC-105, from Table 2, it can be seen that titration results show PBC's and PBC-105
Co element average valence ratio is 1:1.034, this 1:1.038 shown with XPS fitting result is consistent substantially.Illustrate PBC
After middle Pr is more than needed, the valence state of its Co element can be significantly improved, increases Co4+Concentration, to improve its chemical property.
The XPS analysis of table 2 PBC and PBC-105 and the non-titration of oxygen
9.TEC test
In order to ensure battery has a high job stability, each component of battery should have good thermomechanical compatibility
Property, it is embodied in the thermal expansion coefficient (TEC) of each material.Figure 16 is what PBC and PBC-105 was carried out within the scope of 200~1000 DEG C
TEC test.As can be seen from Fig., for PBC, the TEC within the scope of 200~1000 DEG C is 22 ' 10 in air atmosphere-6 K-1, maximum value is 29.5 ' 10-6 K-1.This is because the loss of spin states transformation and Lattice Oxygen under high temperature, cobalt-based calcium titanium
Pit wood material typically exhibits higher TEC.From in figure it can also be seen that for PBC-105, in air atmosphere 200~
TEC value ratio PBC within the scope of 1000 DEG C is more slightly higher, average 25 ' 10-6 K-1.A Pr in PBC are found in characterization before
Make its Co after more than needed4+Concentration increases, and can make the release of the Lattice Oxygen when increasing temperature, and cobalt ions is from Co4+To Co3+Valence state
Variation is bigger, so that Co-O key weakens, it is bigger so as to cause the TEC ratio PBC of PBC-105.
10. impedance and activation energy characterization
Figure 17 is the EIS test result that PBC series cathode is carried out at 600 DEG C.From test result as can be seen that the resistance of PBC
Resist for 0.081 Ω cm2Left and right, the impedance of PBC-095 are 0.068 Ω cm2.And PBC-105 is only in 600 DEG C of impedance
0.046 Ω cm2.This result is also smaller than the PBC-095 impedance that document report is crossed, and illustrates that A Pr are more than needed than A in PBC
Pr defect is advantageously.Figure 18 is what PBC series cathode was calculated according to the EIS result tested within the scope of 550~750 DEG C
Ek figure.As we can clearly see from the figure, the activation energy of PBC-105 is 118 kJ mol-1, 126 kJ than PBC-095 and PBC
mol-1With 133 kJ mol-1Will be low, illustrating in PBC that A Pr are more than needed can be significantly reduced its activation energy.
Figure 19 is the Symmetrical cells that prepare by electrolyte of SDC of PBC-105 600oWith 60 ml min under C-1Air
The impedance stability figure of 200 h is tested under flow velocity.From the graph, it is apparent that PBC-105 is surveyed by the long-time of 200 h
After examination, impedance illustrates that PBC-105 is with good stability as cathode material, is suitable as middle low-temperature solid there is no increasing
Oxide body fuel battery cathode material.
11. output power characterizes
Figure 20 and 21 be respectively PBC and PBC-105 prepared using Ni-YSZ as anode-supported monocell (Ni-YSZ | | YSZ |
| SDC | | cathode) within the scope of 500 ~ 750 DEG C carry out I-V-P test.From test result as can be seen that PBC-105 exists
At 500,550,600,650,700 and 750 DEG C, the case where OCV is respectively 1.16,1.15,1.14,1.12,1.110 and 1.07
Under, output power reaches 0,1,0.3,0.7,1.2,1.9 and 2.5 W cm-2.Comparison discovery, PBC-105 output power are much big
In the output power in OCV close to PBC in situation.Figure 22 and Figure 23 is respectively PBC and PBC-105 in I-V-P test process
The electrochemical impedance spectroscopy of test.From test result as can be seen that both in low temperature impedance it is unobvious, but at high temperature, PBC-
105 total impedance is obviously more much lower than PBC.This is tested with I-V-P and Symmetrical cells EIS test result is consistent before, explanation
Its chemical property can be significantly improved after A Pr are rich in PBC.
Figure 24 and 25 be respectively using PBC-105 as cathode, Ni-SDC be anode-supported preparation monocell (Ni-SDC | |
SDC | | PBC-105) I-V-P that is tested within the scope of 450~650 DEG C and EIS figure.It can be seen from the figure that PBC-105 exists
Output power at 600 DEG C reaches 1.1 W cm-2.Figure 26 be the monocell that is prepared using PBC-105 as cathode at 550 DEG C with
600 mA cm-2Under conditions of the stability test of 50 h that carries out.Find out from test result, PBC-105 has in middle low temperature
It is high performance at the same also have certain stability, be suitable as intermediate temperature solid oxide fuel cell cathode material.
12.SEM characterization
The region a and the region b in Figure 27 is respectively with Ni-YSZ | | YSZ | | SDC | | cutting after the monocell test of PBC preparation
The SEM of face and cathode surface figure.The region c and the region d are with Ni-YSZ | | YSZ | | SDC | | the monocell test of PBC-105 preparation
The SEM figure in section and cathode surface afterwards.It can be seen from the figure that the monocell of PBC and PBC-105 preparation is in electrolyte thickness
Under the premise of being consistent, cell cathode and electrolyte can be in close contact after test, do not generated and fallen off, this is that battery has height
The premise of performance.
It is tested by above characterization, it can be seen that A Pr have more than needed come the method for improving its chemical property.It is right
The phase structure of PBC-105 and PBC carries out analysis and finds, A Pr more than needed are not the Pr for existing in the form of PrOx, but having more than needed
Instead of the position Ba for being all A.It is found through experiments that, after A Pr are more than needed in PBC, its conductivity can be significantly improved, oxygen passes
Movement Capabilities, chemical property etc..The Symmetrical cells that PBC-105 is prepared as electrode are 600oThe impedance of C is only 0.046 Ω
cm2, 0.081 Ω cm with PBC2It compares, reduces by about one time, activation energy is compared and is also substantially reduced.Using Ni-SDC as anode branch
Support monocell (Ni-SDC | | SDC | | PBC-105) 600 DEG C when output power be up to 1.1 W cm-2, illustrate to make in PBC
Its electro-catalysis ability can be significantly improved by obtaining after A Pr have more than needed, and it is potential to become intermediate temperature solid oxide fuel cell
Cathode material.
Claims (5)
1. a kind of cathode material for solid-oxide fuel cell, which is characterized in that it is AA ' B that it, which forms general formula,2O6-δ, molecular formula are as follows:
Pr1+xBaCo2O6-δ, wherein x represents the surplus capacity of Pr, and δ is Lacking oxygen content；X value range is 0.05；The solid oxidation
The preparation method of object fuel battery cathode material includes the following steps: Pr (NO3)3·6H2O、Ba(NO3)2With Co (NO3)2·
6H2O is stoichiometrically added into deionized water, heats and stirs evenly；Ethylenediamine tetra-acetic acid and citric acid are added, it
The pH that ammonium hydroxide is added dropwise to solution afterwards is so that moisture evaporation is obtained spawn under conditions of heating stirring between 6~7；It will
Spawn is placed in baking oven and is dried, and obtains the presoma of cell cathode, then presoma is calcined in Muffle furnace, obtains
To required battery cathode material.
2. cathode material for solid-oxide fuel cell according to claim 1, which is characterized in that ethylenediamine tetra-acetic acid and
The molar ratio of the integral molar quantity of citric acid and Pr, Ba, Co is 2:1:1.
3. cathode material for solid-oxide fuel cell according to claim 2, which is characterized in that the drying course
Condition be 150~250 DEG C of 2~8 h of processing；The condition of the calcination process is 950~1150 DEG C of 3~10 h of calcining.
4. cathode material for solid-oxide fuel cell described in claim 1 is solidifying the application in oxide fuel cell.
5. application according to claim 4, which is characterized in that the anode material in solid oxide fuel cell is NiO
The composite anode formed with SDC or YSZ by the mass ratio of 6:4；Electrolyte in solid oxide fuel cell is SDC.
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| CN103700866A (en) * | 2014-01-09 | 2014-04-02 | 黑龙江大学 | Absent double-perovskite structured negative electrode material of middle-temperature solid oxide fuel battery and preparation method for material |
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| CN103700866A (en) * | 2014-01-09 | 2014-04-02 | 黑龙江大学 | Absent double-perovskite structured negative electrode material of middle-temperature solid oxide fuel battery and preparation method for material |
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| "Evaluation of Pr1+xBa1-xCo2O5+δ(x=0-0.30) as cathode materials forsolid-oxide fuel cells";Long Jiang et al.;《Electrochimica Acta》;20140420;第133卷;第364页摘要部分以及第5段、第365页第1-2、6-7段，第366页第1-2段，第367页第1-2段，第368页第1-3段，第369页第1-6段、第370也第1-3段以及表1-2、图4-6、8和10 |
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