CN103208634B - For the composite cathode material of middle low-temperature protonic transmission Solid Oxide Fuel Cell - Google Patents
For the composite cathode material of middle low-temperature protonic transmission Solid Oxide Fuel Cell Download PDFInfo
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- CN103208634B CN103208634B CN201310097247.5A CN201310097247A CN103208634B CN 103208634 B CN103208634 B CN 103208634B CN 201310097247 A CN201310097247 A CN 201310097247A CN 103208634 B CN103208634 B CN 103208634B
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- Y02E60/30—Hydrogen technology
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Abstract
The invention discloses a kind of composite cathode material of middle low-temperature protonic transmission Solid Oxide Fuel Cell, belong to fuel cell field.The invention is characterized in: utilize the BaCo with higher oxygen ion and electronic conductivity
0.7fe
0.22nb
0.08o
3-δwith the BaZr of high proton conductance
0.1ce
0.7y
0.1yb
0.1o
3-δmutual compound prepares novel cathode material, and its chemical formula is BaCo
0.7fe
0.22nb
0.08o
3-δ-BaZr
0.1ce
0.7y
0.1yb
0.1o
3-δ, wherein the ratio of two-phase can change.Cathode material of the present invention may be used for middle low-temperature protonic transmission Solid Oxide Fuel Cell.BaCo
0.7fe
0.22nb
0.08o
3-δwith BaZr
0.1ce
0.7y
0.1yb
0.1o
3-δafter compound, cathode material has oxonium ion, proton and Electronic Transport of Two Benzene simultaneously, and three phase boundary is expanded, and electrode performance is good, and wherein two-phase has good chemical compatibility, stable performance, BaCo
0.7fe
0.22nb
0.08o
3-δthe existence of mutually middle Co makes electrode material have good electrocatalysis characteristic, can reduce the interface resistance of battery, improves the operating characteristic of battery.
Description
Technical field
The invention belongs to fuel cell field, being specifically related to a kind of BaCo by having higher oxygen ion and electronic conductivity
0.7fe
0.22nb
0.08o
3-δwith the BaZr with high proton conductor rate
0.1ce
0.7y
0.1yb
0.1o
3-δcompound and the high-performance composite cathode material for proton transport Solid Oxide Fuel Cell formed.
Background technology
Traditional Solid Oxide Fuel Cell, due to high operating temperature, makes it propose comparatively harsh requirement to electrode material and connecting material, the problem such as cause its poor stability and the life-span is short, significantly limit its commercialized development process.Therefore reduce operating temperature, exploitation intermediate temperature solid oxide fuel cell becomes the main trend of current Solid Oxide Fuel Cell development.
Solid Oxide Fuel Cell is mainly divided into traditional oxygen ion transport Solid Oxide Fuel Cell (O-SOFC) and the large class of proton transport Solid Oxide Fuel Cell (H-SOFC) two.Compared with oxygen ions migrate activation energy in O-SOFC, in H-SOFC, the transmission activation energy of proton is lower, and therefore, H-SOFC can work at a lower temperature.Meanwhile, according to the operation principle of H-SOFC, the water byproduct of reaction is at cathode side but not the anode-side of O-SOFC produces, and thus can save the water treatment procedure of O-SOFC, simplified apparatus constructs, and improves SOFC operating efficiency.Thus, H-SOFC becomes one of the research emphasis in exploitation intermediate temperature solid oxide fuel cell field.
Cathode material is one of critical material determining cell integrated performance, and in SOFC, cathode material needs in oxidizing atmosphere, to have higher structural stability, stronger catalytic activity and higher electronic conductance and ionic conductance etc.Compared with O-SOFC cathode material, about the kind of H-SOFC cathode material and correlation theory development more late.Therefore, no matter from practical application or theoretical research aspect, H-SOFC mainly follows the related content of O-SOFC.But in fact, for the selection of cathode material, its operation principle need be considered, the problem such as action function and operational environment simultaneously.Different from O-SOFC, in H-SOFC, the process such as generation diffusion of water occurs in cathode side, therefore require with O-SOFC that cathode material preferably has oxonium ion and compares with the requirement of the transmittability of electronics, H-SOFC also requires that cathode material preferably possesses the transmittability of proton simultaneously, namely has the transmittability of good proton, oxonium ion and electronics simultaneously.
With regard to the current research to H-SOFC, cathode material more common at present mainly contains electronic conductor, oxonium ion-electron mixed conductor and protonic-electronic mixed conductor etc.First kind electronic conductor cathode material only conduction electron, as La
1- xsr
xmnO
3-δ(LSM), the high (>100Scm of electronic conductivity
-1), but its ionic conductivity is very low, and 900
o5.9 × 10 are only during C
-7scm
-1a kind of simple electronic conductor (I.Yasuda, K.Ogasawara, etal.SolidStateIonics86-88 (1996): 1197-1201), electronic energy is only had to realize body diffusion in this kind of material, and oxonium ion and proton are only diffusion into the surfaces, therefore its three phase boundary region is very limited.Equations of The Second Kind is oxonium ion-electron mixed conductor, such as Ca-Ti ore type La
l-xsr
xcoO
3-δ(LSC) (R.A.DeSouza, J.A.Kilner.SolidStateIonics106 (1998): 175-187), this kind of material has higher electronic conductance and oxygen-ion conduction simultaneously, but the limited transmission of its proton, its three phase boundary region is also less, is unfavorable for improving its electrochemical reaction speed.3rd class is protonic-electronic mixed conductor, only has the different materials of minority at present, such as the BaCeO of B position doped F e, Bi element
3base cathode material (Z.Tao, L.Bi, etal.ElectrochemistryCommunication11 (2009): 688-690), but due to the limited transmission of oxonium ion in such material, three phase boundary can not be expanded, and the performance of electrode is affected.
If H-SOFC cathode material possesses oxonium ion, proton, electronic conductivity simultaneously, so three phase boundary will be expanded greatly, oxonium ion, and the diffusion length of proton and electronics will shorten greatly, and the dynamic process of electrode reaction will be accelerated.If cathode material possesses the catalytic performance of good stability in addition simultaneously, so the job stability of electrode and electrochemical reaction speed all can ensure to some extent.Thus the present invention have selected the BaCo with higher oxygen ion and electronic conductance, better catalytic activity
0.7fe
0.22nb
0.08o
3-δwith the BaZr had compared with high proton conductivity
0.1ce
0.7y
0.1yb
0.1o
3-δcarry out compound, prepare the high performance cathodes material for H-SOFC.
Summary of the invention
The object of the invention is to prepare a kind of Novel oxygen ion-protonic-electronic conduction composite cathode material with high catalytic activity.Scheme is by oxonium ion-electronic conductor phase and proton conductor phase compound, expands the phase reaction region of electrode, thus reduces electrode polarization, accelerating electrode electrochemical reaction process, improves the power output of battery.
The present invention will be by having the oxonium ion-electronic conductor phase BaCo of hyperoxia ion surface exchange coefficient, high oxonium ion and electronic conduction ability
0.7fe
0.22nb
0.08o
3-δwith the proton conductor phase BaZr of high proton conducting power
0.1ce
0.7y
0.1yb
0.1o
3-δcompound and form BaCo
0.7fe
0.22nb
0.08o
3-δ-BaZr
0.1ce
0.7y
0.1yb
0.1o
3-δcomposite cathode material.
This composite cathode material is used for middle low-temperature protonic transmission Solid Oxide Fuel Cell, 750
oin C wet air atmosphere, BaCo
0.7fe
0.22nb
0.08o
3-δcontent is the composite cathode of 60wt%, and area specific resistance is 0.35 cm
2.750
ounder the probe temperature of C, with the BaZr of 60 μm of thickness
0.1ce
0.7y
0.1yb
0.1o
3-δfor electrolyte, NiO-BaZr
0.1ce
0.7y
0.1yb
0.1o
3-δfor anode, BaCo
0.7fe
0.22nb
0.08o
3-δthe BaCo of content 60wt%
0.7fe
0.22nb
0.08o
3-δ-BaZr
0.1ce
0.7y
0.1yb
0.1o
3-δfor negative electrode form anode-supported cells peak power output be 123mWcm
-2.
The material provided in the present invention can be prepared as follows:
A, BaCo
0.7fe
0.22nb
0.08o
3-δpowder adopts Solid phase synthesis.Stoichiometrically take appropriate BaCO
3, Nb
2o
5, Fe
2o
3, Co (CH
3cOO)
24H
2o is raw material, is medium, raw mixture is put into ZrO with alcohol
2ball milling 4 ~ 8h in ball ball grinder, rotating speed is 200 ~ 600r/min, and raw material is mixed, and mixture suspension-turbid liquid is placed in glass dish, after drying in an oven, through 900 ~ 1300
oc heat treatment 8 ~ 12h, obtains pure phase perovskite structure oxide, then the oxide obtained is put into ball grinder grinding 2 ~ 6h, the BaCo obtained
0.7fe
0.22nb
0.08o
3-δthinner powder is as the oxonium ion-proton phase of composite cathode.
B, BaZr
0.1ce
0.7y
0.1yb
0.1o
3-δemploying citric acid-nitrate method synthesizes.By appropriate Yb
2o
3be dissolved in concentrated nitric acid solution, heating water bath, until completely dissolved, stoichiometrically by Ba (NO
3)
2, Ce (NO
3)
36H
2o, Zr (NO
3)
45H
2o and Y (NO
3)
36H
2o adds in this nitrate solution, in order to complexing is complete, ethylenediamine tetra-acetic acid (EDTA) and monohydrate potassium add in solution as complexing agent simultaneously, wherein the proportion of metal ion and citric acid is 1:1 ~ 1:2, the ratio of metal ion and EDTA is 1:0.8 ~ 1:1.2, pH is adjusted to 7 ~ 9, utilizes magnetic stirring apparatus to be mixed by solution, 20 ~ 90
oc heating water bath makes unnecessary moisture evaporation, obtains gel liquid; This gel liquid is put into porcelain unit ware, resistance wire furnace heats, until it burns completely, obtain oxide precursor, presoma is 800 ~ 1200
oprocess 4 ~ 8h in air atmosphere under C, obtain the BaZr of single Perovskite Phase
0.1ce
0.7y
0.1yb
0.1o
3-δ.
C, be medium with absolute ethyl alcohol, be the two-phase mixtures of 3:7 ~ 7:3 by mass ratio, be ground in mortar evenly, obtain composite cathode material.
D, in gained composite cathode material fine powder, add the inflammable substance of 10 ~ 50vol%, inflammable substance comprises carbon dust, starch, corn flour, resin, then dry-pressing or half dry-pressing formed, then in 1050 ~ 1350
oc temperature lower calcination 2 ~ 6h, can prepare porous cathode block; Or make slurry by adding water, soluble starch and ethyl cellulose in gained composite cathode powder, adopt silk screen print method it to be coated in equably fine and close BaZr
0.1ce
0.7y
0.1yb
0.1o
3-δelectrolyte sheet surface, through 1050 ~ 1350
oc temperature lower calcination 2 ~ 6h, makes the BaCo of porous
0.7fe
0.22nb
0.08o
3-δ-BaZr
0.1ce
0.7y
0.1yb
0.1o
3-δcomposite cathode film.
The invention has the advantages that, prepare a kind of novel composite cathode material BaCo for middle low-temperature protonic transmission Solid Oxide Fuel Cell
0.7fe
0.22nb
0.08o
3-δ-BaZr
0.1ce
0.7y
0.1yb
0.1o
3-δ.Oxonium ion-electronic conductor is wherein the BaCo containing Co mutually
0.7fe
0.22nb
0.08o
3-δ.Generally, containing Co material, all there is good electrocatalysis characteristic.Large to the general thermal coefficient of expansion containing the appearance of Co material in addition, the problems such as structural instability, research shows at BaCoO
3-δthe a small amount of Fe and micro-Nb that adulterates in matrix forms BaCo
0.7fe
0.22nb
0.08o
3-δtime, appropriate doping effectively can suppress the phase transformation of material, material is made still to remain cubic perovskite structure when room temperature, higher oxygen vacancy concentration can be produced at material simultaneously, to promote the conduction (Y.F.Cheng of oxonium ion, H.L.Zhao, etal.JournalofMembraneScience322 (2008): 484-490).In addition, the high electro catalytic activity that material has, high oxygen ion conduction ability, has remarkable facilitation to the raising of electrode performance, as taken SDC as electrolyte, BaCo
0.7fe
0.22nb
0.08o
3-δas showing higher electrode performance (C.J.Zhu, X.M.Liu, etal.ElectrochemistryCommunications11 (2009): 958-961) during negative electrode.Meanwhile, the proton conductor in the present invention is BaZr mutually
0.1ce
0.7y
0.1yb
0.1o
3-δ, its proton conductivity is higher than traditional oxygen ion conductor electrolyte and conventional proton conductor BaZr
0.1ce
0.7y
0.2o
3-δ, and there is good sulfur poisoning-resistant and Carbon deposition phenomenon.This composite cathode material has concentrated the advantage of bi-material, its preparation method mixes electrolyte in traditional cathode material in addition, the thermal coefficient of expansion of adjustable electrode, strengthen the bond strength of itself and electrolyte membrance, increase its job stability, meanwhile, compound reaches again the effect of expansion three-phase reaction interface.
Accompanying drawing explanation
Fig. 1 is BaZr
0.1ce
0.7y
0.1yb
0.1o
3-δpowder 1000
o6h, BaCo is calcined under C
0.7fe
0.22nb
0.08o
3-δpowder 1100
o10h and BaCo is calcined under C
0.7fe
0.22nb
0.08o
3-δcontent is the BaCo of 50wt%
0.7fe
0.22nb
0.08o
3-δ-BaZr
0.1ce
0.7y
0.1yb
0.1o
3-δcomposite cathode material 1200
othe X-ray diffraction curve chart after 3h is calcined under C;
Fig. 2 is the BaCo of different ratio
0.7fe
0.22nb
0.08o
3-δ-BaZr
0.1ce
0.7y
0.1yb
0.1o
3-δthe Symmetrical cells polarization resistance that composite cathode material forms and probe temperature graph of a relation.
Embodiment
Below in conjunction with embodiment, the present invention will be further described, but be not limited to protection scope of the present invention:
Embodiment 1:BaCo
0.7fe
0.22nb
0.08o
3-δaccount for synthesis and the chemical compatibility test of the composite cathode material of 50wt%
By BaCo
0.7fe
0.22nb
0.08o
3-δstoichiometric proportion, take appropriate BaCO
3, Nb
2o
5, Fe
2o
3, Co (CH
3cOO)
24H
2o is raw material, is medium, raw mixture is put into ZrO with alcohol
2ball milling 6h in ball ball grinder, rotating speed is 400r/min, and raw material is mixed, and mixture suspension-turbid liquid is placed in glass dish, after drying in an oven, through 1100
oc heat treatment 10h, obtains pure phase perovskite structure oxide, then the oxide obtained is put into ball grinder grinds 4h, obtains thinner powder as the oxonium ion prepared required for composite cathode-proton phase BaCo
0.7fe
0.22nb
0.08o
3-δ.Preparation BaZr
0.1ce
0.7y
0.1yb
0.1o
3-δ, take appropriate Yb
2o
3, by Yb
2o
3be dissolved in concentrated nitric acid solution, heating water bath, until completely dissolved, stoichiometrically by Ba (NO
3)
2, Ce (NO
3)
36H
2o, Zr (NO
3)
45H
2o and Y (NO
3)
36H
2o adds in this nitrate solution, and in order to complexing is complete, EDTA and monohydrate potassium add in solution as complexing agent simultaneously, by metal ion, the ratio of citric acid and EDTA is that the ratio of 1:1.5:1 adds in the above-mentioned aqueous solution, and pH is adjusted to 8, magnetic stirring apparatus is utilized to be mixed by solution, 80
oc heating water bath makes unnecessary moisture evaporation, obtains gel liquid; This gel liquid is put into porcelain unit ware, resistance wire furnace heats, until it burns completely, obtain oxide precursor, presoma is 1000
oprocess 6h in air atmosphere under C, obtain single Perovskite Phase BaZr
0.1ce
0.7y
0.1yb
0.1o
3-δ.
After two powder synthesis, taking two kinds of materials of equal in quality, is medium with absolute ethyl alcohol, and by two-phase mixtures, be ground in mortar evenly, obtain composite cathode material, obtain flake shaped base substrate by dry-pressing formed, base substrate is 1200
ocalcine 3h under C, XRD testing result display (as shown in Figure 1), occur without obvious impurity peaks after composite material calcining, illustrate that two-phase is 1200
owithout significant reaction within the scope of C, there is good chemical compatibility.
Embodiment 2: the BaCo of two-phase different ratio
0.7fe
0.22nb
0.08o
3-δ-BaZr
0.1ce
0.7y
0.1yb
0.1o
3-δthe test of polarization resistance
Two phase material is pressed BaZr
0.1ce
0.7y
0.1yb
0.1o
3-δ: BaCo
0.7fe
0.22nb
0.08o
3-δmass ratio 6:4,5:5 and 4:6 mix and obtain composite cathode powder.By composite cathode powder and pore creating material soluble starch, 8:2 mixes in mass ratio, in this powder, then adds terpinol containing 10% ethyl cellulose as binding agent, the mass ratio 6:4 of powder and binding agent.Mixture is fully ground, until obtain even thick cathode material slurry.By silk screen print method, slurry is evenly coated on fine and close BaZr
0.1ce
0.7y
0.1yb
0.1o
3-δelectrolyte sheet surface, after drying in an oven, puts into high temperature furnace 1200
oc temperature lower calcination 3h, obtains Symmetrical cells.
Symmetrical cells is carried out to the test of electrochemical impedance spectroscopy, the instrument of employing is Solartron1260 frequency response analyzer, utilizes 1287 electrochemical interfaces to characterize electrode polarization process and electrode material electric conductivity.Symmetrical cells is respectively 550,600,650,700 and 750
otest under the probe temperature of C, disturbance voltage is 5mV, and frequency range is 1MHz ~ 0.01Hz.Utilize ZsimpWin software to carry out matching to the data obtained, through the analysis of data, obtain the Arrhenius curve of polarization resistance, as shown in Figure 2, along with BaCo in composite cathode
0.7fe
0.22nb
0.08o
3-δincreasing of content, interface resistance reduces gradually.750
oin C wet air atmosphere, BaCo
0.7fe
0.22nb
0.08o
3-δcomposite cathode when content is 60wt%, its area specific resistance is 0.35 cm
2.
Embodiment 3: the preparation of the anode-supported cells that the combination electrode of different ratio forms and voltage-current density-power density curve test
4:6:2 is by BaCe in mass ratio
0.7zr
0.1y
0.1yb
0.1o
3-δ, NiO and soluble starch mix, and be that medium carries out ball milling, obtain anode powder after oven dry with absolute ethyl alcohol, add appropriate PVA and carry out dry-pressing formed in anode powder, evenly sieve spill a small amount of electrolyte powder BaCe in shaping anode base substrate side
0.7zr
0.1y
0.1yb
0.1o
3-δ, secondary dry-pressing formed formation anode-electrolyte dual-layer green body, through 1350
oc high-temperature calcination obtains the circular film of electrolyte densification.
Two phase material is pressed BaZr
0.1ce
0.7y
0.1yb
0.1o
3-δ: BaCo
0.7fe
0.22nb
0.08o
3-δmass ratio 6:4,5:5 and 4:6 mix and obtain composite cathode powder.By composite cathode powder and pore creating material soluble starch, 8:2 carries out Homogeneous phase mixing in mass ratio, then in the powder mixed, add mixed solution containing the terpinol of 10% ethyl cellulose as binding agent, powder and binding agent ratio are mass ratio 6:4.Mixture is fully ground, until obtain even thick cathode material slurry.
Silk screen print method is utilized thick cathode slurry to be evenly coated on electrolyte.By gained base substrate 1200
oc, calcines 2h under air atmosphere, obtains anode supported cells.Utilize platinum to starch as collector and bridging agent, wire is connected with cathode and anode.Waterglass (Cerama-bond552-VFG, Aremco) is adopted to encapsulate battery under high temperature.Alumina ceramic tube one end being fixed with battery puts into resistance furnace, and adjustment position, makes it be in the zone of constant temperature place of resistance furnace, be connected with external circuit.Raised temperature, surveys at the anode of battery the H passing into water
2as fuel gas, flow is 60mlmin
-1, cathode side passes into natural air.In experimentation, by changing external circuit loading condition, under test different loads, both end voltage and electric current obtain the output performance of battery, obtain voltage-current density-power density curve, 750 to data after processing
oin C wet air, with the BaZr of 60 μm of thickness
0.1ce
0.7y
0.1yb
0.1o
3-δfor electrolyte, NiO-BaZr
0.1ce
0.7y
0.1yb
0.1o
3-δfor anode, BaCo
0.7fe
0.22nb
0.08o
3-δthe BaCo of content 60wt%
0.7fe
0.22nb
0.08o
3-δ-BaZr
0.1ce
0.7y
0.1yb
0.1o
3-δfor negative electrode form anode-supported cells peak power output maximum, be 123mWcm
-2.
Claims (2)
1., for a composite cathode material for middle low-temperature protonic transmission Solid Oxide Fuel Cell, it is characterized in that: by oxonium ion-electronic conductor phase BaCo
0.7fe
0.22nb
0.08o
3-δwith proton conductor phase BaZr
0.1ce
0.7y
0.1yb
0.1o
3-δmutually be compounded to form composite cathode material BaCo
0.7fe
0.22nb
0.08o
3-δ-BaZr
0.1ce
0.7y
0.1yb
0.1o
3-δ, wherein the excursion of two-phase mass ratio is 3:7 ~ 7:3; The described composite cathode material for middle low-temperature protonic transmission Solid Oxide Fuel Cell prepares by the following method, comprises step:
A, BaCo
0.7fe
0.22nb
0.08o
3-δpowder adopts Solid phase synthesis: stoichiometrically take appropriate BaCO
3, Nb
2o
5, Fe
2o
3, Co (CH
3cOO)
24H
2o is raw material, is medium, raw mixture is put into ZrO with alcohol
2ball milling 4 ~ 8h in ball ball grinder, rotating speed is 200 ~ 600r/min, raw material is mixed, mixture suspension-turbid liquid is placed in glass dish, after drying in an oven, through 900 ~ 1300 DEG C of heat treatment 8 ~ 12h, obtain pure phase perovskite structure oxide, again the oxide obtained is put into ball grinder grinding 2 ~ 6h, the BaCo obtained
0.7fe
0.22nb
0.08o
3-δthinner powder is as the oxonium ion-proton phase of composite cathode;
B, BaZr
0.1ce
0.7y
0.1yb
0.1o
3-δemploying citric acid-nitrate method synthesizes: by appropriate Yb
2o
3be dissolved in concentrated nitric acid solution, heating water bath, until completely dissolved, stoichiometrically by Ba (NO
3)
2, Ce (NO
3)
36H
2o, Zr (NO
3)
45H
2o and Y (NO
3)
36H
2o adds in this nitrate solution, in order to complexing is complete, ethylenediamine tetra-acetic acid (EDTA) and monohydrate potassium add in solution as complexing agent simultaneously, wherein the proportion of metal ion and citric acid is 1:1 ~ 1:2, the ratio of metal ion and EDTA is that 1:0.8 ~ 1:1.2, pH are adjusted to 7 ~ 9, utilizes magnetic stirring apparatus to be mixed by solution, make unnecessary moisture evaporation at 20 ~ 90 DEG C of heating water baths, obtain gel liquid; This gel liquid is put into porcelain unit ware, resistance wire furnace heats, until it burns completely, obtains oxide precursor, presoma processes 4 ~ 8h in air atmosphere at 800 ~ 1200 DEG C, obtains the BaZr of single Perovskite Phase
0.1ce
0.7y
0.1yb
0.1o
3-δ;
C, be medium with absolute ethyl alcohol, be the two-phase mixtures of 3:7 ~ 7:3 by mass ratio, be ground in mortar evenly, obtain composite cathode material.
2. BaCo according to claim 1
0.7fe
0.22nb
0.08o
3-δ-BaZr
0.1ce
0.7y
0.1yb
0.1o
3-δthe purposes of composite cathode material, this material is used for middle low-temperature protonic transmission Solid Oxide Fuel Cell.
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| CN103825039A (en) * | 2014-02-27 | 2014-05-28 | 盐城工学院 | Electrolyte material and preparation method for intermediate and low-temperature solid oxide fuel cells |
| CN103811788A (en) * | 2014-02-27 | 2014-05-21 | 盐城工学院 | Preparation method for middle-temperature and low-temperature solid oxide fuel battery |
| WO2016157566A1 (en) * | 2015-03-30 | 2016-10-06 | 住友電気工業株式会社 | Proton conductor, fuel-cell solid-electrolyte layer, cell structure, and fuel cell provided with same |
| CN106876755B (en) * | 2015-12-12 | 2019-07-02 | 中国科学院大连化学物理研究所 | A kind of method of low-firing composite cathode on cerium base electrolyte interlayer |
| CN106784864A (en) * | 2016-12-22 | 2017-05-31 | 中国矿业大学 | A kind of barium zirconium yttrium mixes cathode material system of cobalt and preparation method thereof |
| CN106784866A (en) * | 2016-12-22 | 2017-05-31 | 中国矿业大学 | Iron-based single phase cathode material system and preparation method with proton-electron hybrid conductive |
| CN109817997B (en) * | 2019-03-20 | 2022-01-28 | 南京工业大学 | Perovskite mixed conductor material and preparation method thereof |
| US11152625B2 (en) * | 2019-08-28 | 2021-10-19 | Robert Bosch Gmbh | Intermediate temperature solid oxide fuel cell cathode material |
| CN110937897B (en) * | 2019-12-24 | 2022-02-01 | 东北大学 | Mixed solid electrolyte proton conductor material and preparation method thereof |
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