CN102683722A - Solid oxide fuel cell composite cathode and preparation method thereof - Google Patents
Solid oxide fuel cell composite cathode and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 36
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 32
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 32
- 238000005245 sintering Methods 0.000 claims abstract description 23
- 239000000725 suspension Substances 0.000 claims abstract description 18
- 239000010406 cathode material Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
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- 239000003792 electrolyte Substances 0.000 claims description 74
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- 239000012071 phase Substances 0.000 claims description 38
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- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 26
- 238000007598 dipping method Methods 0.000 claims description 20
- 239000000284 extract Substances 0.000 claims description 18
- 238000002803 maceration Methods 0.000 claims description 18
- 239000012528 membrane Substances 0.000 claims description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000004094 surface-active agent Substances 0.000 claims description 14
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- 239000004020 conductor Substances 0.000 claims description 13
- 239000010416 ion conductor Substances 0.000 claims description 13
- 239000011159 matrix material Substances 0.000 claims description 12
- 229910021645 metal ion Inorganic materials 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000007790 solid phase Substances 0.000 claims description 10
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- 239000003960 organic solvent Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000008139 complexing agent Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 229960001484 edetic acid Drugs 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- 238000003980 solgel method Methods 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- ISSXKNWTCLRPJY-UHFFFAOYSA-N O.O.[O-2].[Zr+4].[O-2] Chemical compound O.O.[O-2].[Zr+4].[O-2] ISSXKNWTCLRPJY-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- IFKAROTVVUBMBY-UHFFFAOYSA-N [Ba].[Ce] Chemical compound [Ba].[Ce] IFKAROTVVUBMBY-UHFFFAOYSA-N 0.000 claims description 2
- ISWNJSHGUJYCFP-UHFFFAOYSA-N [Ce].[Sr] Chemical compound [Ce].[Sr] ISWNJSHGUJYCFP-UHFFFAOYSA-N 0.000 claims description 2
- CAGZNTXUZUOERQ-UHFFFAOYSA-N [O-2].O.[Ce+3] Chemical compound [O-2].O.[Ce+3] CAGZNTXUZUOERQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- YIMPFANPVKETMG-UHFFFAOYSA-N barium zirconium Chemical compound [Zr].[Ba] YIMPFANPVKETMG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004567 concrete Substances 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 2
- PDGYMUBNWUUWEI-UHFFFAOYSA-N strontium zirconium Chemical compound [Sr].[Zr] PDGYMUBNWUUWEI-UHFFFAOYSA-N 0.000 claims description 2
- 239000010409 thin film Substances 0.000 abstract description 28
- 239000000463 material Substances 0.000 abstract description 9
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- 230000002238 attenuated effect Effects 0.000 abstract 1
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- 229910002806 Sm0.2Ce0.8O1.9 Inorganic materials 0.000 description 9
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- 229910021641 deionized water Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000010304 firing Methods 0.000 description 6
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- 230000000930 thermomechanical effect Effects 0.000 description 5
- 229910002939 BaZr0.8Y0.2O3−δ Inorganic materials 0.000 description 4
- 229910002607 Gd0.1Ce0.9O1.95 Inorganic materials 0.000 description 4
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- 101150058765 BACE1 gene Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention belongs to the field of solid oxide fuel cells and particularly relates to a solid oxide fuel cell composite cathode and a preparation method thereof, wherein the solid oxide fuel cell composite cathode has a high electrochemistry performance and is stable in long-time operation. The preparation method includes the following steps of step one, preparing a three-dimensional porous skeleton made of electrolytic materials at a high temperature; step two, preparing a powder suspension or a nitrate solution of a cathode material; step three, impregnating the powder suspension or the nitrate solution into the porous skeleton and then calcinating the porous skeleton; step four, repeating the operation of the step 3 for a plurality of times until the impregnating quantity reaches the requirement; step five, performing high temperature sintering under an air atmosphere to obtain the three-dimensional composite cathode with a core-shell structure. According to the solid oxide fuel cell composite cathode and the preparation method thereof, the process is simple, expensive experiment apparatuses are not required, the obtained composite cathode is of the core-shell structure, a core is the electrolytic skeleton, a shell is a phase reaction layer with a stable nano thin film structure, and the problem that the performance is attenuated due to the fact that nano particles of the solid oxide fuel cell composite cathode prepared by an impregnating method are low in stability and easy to sinter is solved.
Description
Technical field
The invention belongs to field of solid oxide fuel, be specifically related to a kind of high electrochemical performance, long-play stable solid oxide fuel battery complex cathode and preparation method thereof.
Background technology
Classical cathode material for solid-oxide fuel cell is the oxide La with perovskite crystal phase structure
0.8Sr
0.2MnO
3(LSM), it has electronic conductivity preferably, with traditional electrolyte than matched coefficient of thermal expansion, and higher thermo-chemical stability etc. still is widely used in high temperature SOFCs at present.Yet because the pure electron conduction characteristic of LSM, electrode reaction is confined on LSM-electrolyte-air three phase boundary.At high temperature, electrode reaction can keep speed faster, so LSM polarization of electrode resistance can be controlled in the reasonable range.Yet along with the reduction of temperature, the active of electrode significantly descends; Below 850 ℃, the electrode polarization resistance that sharply increases makes the power output of battery not have the value of practical application.People attempt to have the apparent oxide ion conduction ability that second of ionic conduction ability improves electrode mutually through introducing in mutually at LSM, make the active potential energy of electrode expand to the inside of electrode, and then improve electrode performance at low temperatures effectively.Because two-phase is by mechanical mixture, the performance of electrode depends on preparation method and condition strongly, and generally speaking, two-phase can only reach the mixing of micron level.Discover that adopt conventional combination electrode, electrode activity still can keep level preferably when operating temperature dropped to 800 ℃ of left and right sides.Yet when temperature further descended, electrode polarization resistance was still bigger.
Because nano material has the characteristic of many excellences, its application in energy storage and Conversion of energy field has in recent years caused that numerous researchers pay close attention to widely.Nano material has been used as the oxygen reduction reaction electrode catalyst of low temperature polymer electrolyte fuel battery widely.In field of solid oxide fuel, nano-electrode has also caused people's interest.The many solid-oxide fuel battery nano particle modifications of research can be divided into four types at present: one, loaded with nano noble metal granule on the electrode; Two, modify nano-oxide particles on the electrode with hyperoxia hole concentration or highly electron conductive; Three, the noble metal that load has the nanometer network structure on the electrolyte skeleton; Four, modify oxide on the electrolyte skeleton with nanometer network structure.The preparation of nano-modified electrode mainly is made up of solution impregnation and two steps of low-temperature sintering.Can have one in the active stephanoporate framework that is incorporated into the high porosity for preparing in advance mutually of high electrode through dipping, and then form two-phase combination electrode with special appearance.Compare with the combination electrode of routine, the coefficient of expansion of the electrode of this immersion process for preparing and skeleton similar, and common combination electrode is the weighted mean of two phases, makes the thermo mechanical stability of electrode strengthen greatly.In addition because special appearance structure adopts less activity substance content also can realize continuous passage.But a shortcoming of infusion process is may cause the serious decline of pores rate, and then the mass transfer generation of electrode is had a strong impact on.In addition, a very big shortcoming is arranged is low thermal stability to nano-electrode.Nano particle is the very high astable material of a kind of surface energy, under the operating temperature of SOFCs, adds the effect of polarization current, and it is very serious that the sintering between nano particle becomes, thereby cause performance significantly to decay.Thereby the application of the negative electrode of traditional immersion process for preparing in SOFCs receives very big restriction.
Summary of the invention
To the deficiency of prior art, the present invention provides a kind of acquisition high electrochemical performance, long-play stable solid oxide fuel battery complex cathode, and another object of the present invention provides the preparation method of above-mentioned composite cathode.
Technical scheme of the present invention is: a kind of compound cathode of solid oxide fuel battery is characterized in that: composite cathode has nucleocapsid structure; Its center is the electrolyte skeleton, and shell is the phase reaction layer of stabilized nano membrane structure, and wherein, the mass fraction that shell accounts for whole composite cathode is 25%-45%; The phase reaction layer is that material and the phase reaction of skeleton generation solid phase behind the dipping generates, and has both contained the element in the maceration extract in this layer, contains the element in the skeleton again.
Preferred electrolyte material skeleton has three-dimensional porous structure, and porosity is 30% ~ 60%; The thickness of electrolyte skeleton is 10 ~ 30 μ m.
Described electrolyte framework material is a kind of of oxygen ion conductor oxide, proton conductor oxide or is the mixed oxide of oxygen ion conductor oxide and proton conductor oxide.
Preferred described oxygen ion conductor oxide is doping of cerium oxide oxygen ion conductor oxide, stable zirconium oxide-oxygen ion conductor oxide, lanthanum gallium based perovskite type oxygen ion conductor oxide or the aluminium base Ca-Ti ore type oxygen ion conductor of lanthanum oxide.Sm more preferably
0.2Ce
0.8O
1.9Or Gd
0.1Ce
0.9O
1.95
Preferred described proton conductor oxide is the sub-conductor oxide of strontium cerium matrix, the sub-conductor oxide of strontium zirconium matrix, the sub-conductor oxide of barium cerium matrix or the sub-conductor oxide of barium zirconium matrix; More preferably BaZr
0.1Ce
0.7Y
0.2O
3-δ, BaCe
0.8Y
0.2O
3-δOr BaZr
0.8Y
0.2O
3-δ
The present invention also provides the preparation method of above-mentioned compound cathode of solid oxide fuel battery, and its concrete steps are following: one, high temperature sintering prepares the three-dimensional porous skeleton that electrolyte is formed; Two, the powder suspension or the precursor nitrate solution of preparation cathode material; Three, powder suspension that obtains in the step 2 or precursor nitrate solution are impregnated in the stephanoporate framework that obtains in the step 1, then at 400 ~ 600 ℃ of roasting 30 ~ 60min; Four, the operation of repeating step three reaches required pickup, i.e. the mass fraction of nano thin-film=nano thin-film quality in the composite cathode/(nano thin-film quality+stephanoporate framework quality)=25%-45%; Five, 1000-1200 ℃ of sintering 30 ~ 300min under the air atmosphere promptly obtains having the three-dimensional composite cathode of nucleocapsid structure.
High temperature of the present invention prepares the conventional method of three-dimensional porous skeleton employing that electrolyte is formed, and preferred sintering temperature is 1250 ~ 1400 ℃, and sintering time is 4 ~ 8h.
The powder suspension of cathode material of the present invention is the suspension that sol-gel process, solid phase method, the powder after the hydrothermal synthesis method preparation and dispersant, organic solvent and the surfactant through routine mixes; Wherein said powder is Ln
xCo
2-xO
y, Ln=Y wherein, La, Pr, Nd, Sm, Gd or Dy, Sr
xCo
2-xO
y, Ba
xCo
2-xO
y, Co
3O
4, Co
2O
3Or one or more of CoO, 1>=x>0,3>=y>2; More preferably described powder is SrCoO
3, Co
3O
4Described organic solvent is ethanol, ethylene glycol, 1, one or more in 2-butanediol or the acetone; Wherein the usage ratio of powder and organic solvent is 80 ~ 120g/L; Described dispersant is polyethylene glycol or polyvinyl alcohol, and wherein dispersant is 1 ~ 3:10 with the volume of organic solvent ratio; Described surfactant is one or more in citric acid, ethylenediamine tetra-acetic acid, urea, glycine or the triethanolamine, and wherein the quality of surfactant is 1 ~ 2 times of powder quality.
The presoma nitrate solution of preferred cathode material is the mixed aqueous solution of nitrate, complexing agent and surfactant; Wherein the concentration of presoma nitrate solution is 0.1 ~ 2mol/L; Preferred described nitrate is Co (NO
3)
3, or Ln (NO
3)
3, Sr (NO
3)
3Or Ba (NO
3)
3In one or more and Co (NO
3)
3Mixing, Co and other metal ions mol ratio be 1: (0.5 ~ 1.5), Ln=Y wherein, La, Pr, Nd, Sm, Gd or Dy; More preferably described nitrate is Co (NO
3)
3, or Co (NO
3)
3And Sr (NO
3)
3The mol ratio of metal ion be 1: mix (0.5 ~ 1.5).Described complexing agent is one or more in citric acid, ethylenediamine tetra-acetic acid, urea or the glycine, and wherein the consumption of complexing agent is 1 ~ 3 times of amount of substance of total metal ion; Described surfactant is an ethanol, and wherein the volume ratio of nitrate solution and ethanol is 1 ~ 4.
In order to reach required pickup, i.e. the mass fraction of nano thin-film=nano thin-film quality in the composite cathode/(nano thin-film quality+stephanoporate framework quality)=25%-45%; The number of operations that generally needs repeating step three is 3 ~ 5 times.
The described high temperature sintering of step 5 is a reaction-sintered, and promptly material and the phase reaction of stephanoporate framework generation solid phase behind the dipping both contained the element in the maceration extract in the phase reaction layer of generation, contained the element in the stephanoporate framework again.
Beneficial effect:
The resulting composite cathode of the present invention also has the advantage of porosity height, Heat stability is good except the advantage of immersion process for preparing composite cathode, thereby guarantees that this composite cathode has high chemical property and long playing stability.
Description of drawings
Fig. 1 is Sm among the embodiment 1
0.2Ce
0.8O
1.9Electrolyte is bone porous microscopic appearance figure.
Fig. 2 is the sketch map of the three-dimensional composite cathode with nucleocapsid structure of embodiment 1 preparation.
Fig. 3 is the Sm of embodiment 2 preparations
0.2Ce
0.8O
1.9Electrolyte is a stephanoporate framework, Co (NO
3)
3And Sr (NO
3)
3Solution is the microscopic appearance figure of the composite cathode of maceration extract.
Fig. 4 is Sm among the embodiment 2
0.2Ce
0.8O
1.9Electrolyte is a stephanoporate framework, Co (NO
3)
3And Sr (NO
3)
3Solution is that the composite cathode of maceration extract is at 700 ℃ electrochemical impedance spectrogram.
Fig. 5 is Sm among the embodiment 2
0.2Ce
0.8O
1.9Electrolyte is a stephanoporate framework, Co (NO
3)
3And Sr (NO
3)
3Solution is that the composite cathode of maceration extract is 700 ℃ long playing performance map.
Fig. 6 is BaZr among the embodiment 3
0.1Ce
0.7Y
0.2O
3-δElectrolyte is a stephanoporate framework, Co (NO
3)
3Solution is the microscopic appearance figure of the composite cathode of maceration extract.
Embodiment
Embodiment 1: preparation is with electrolyte Sm
0.2Ce
0.8O
1.9Be stephanoporate framework, SrCoO
3Powder suspension is the composite cathode of maceration extract.
Step is following:
(1) the three-dimensional porous electrolyte skeleton of preparation: with electrolyte Sm
0.2Ce
0.8O
1.9Do stephanoporate framework; The detailed making step of skeleton is seen and is delivered document: F.Zhao, R.R.Peng, C.R.Xia; The firing temperature of skeleton is 1250 ℃/5h in Fuel Cells Bull.2 (2008) the 12-16. present embodiment, obtains the three-dimensional porous electrolyte skeleton of thick 20 μ m porositys 50%.
Shown in Figure 1 is Sm
0.2Ce
0.8O
1.9Electrolyte is bone porous microscopic appearance figure; As can be seen from the figure: the skeleton of this method preparation is satisfactory for result, pore-size distribution homogeneous comparatively in the skeleton, and pore size is suitable, is suitable for dipping.
(2) the powder suspension of preparation cathode material: cathode powder SrCoO
3-δAdopt conventional sol-gel process synthetic, see document for details: Y.B.Zhou, B.M.An, Y.M.Guo, R.Ran, Z.P.Shao, Electrochem.Commun.11 (2009) 2216-2219. is then with 1g SrCoO
3Powder, 10ml ethanol, 2ml polyethylene glycol and 1.5g glycine are put into ball grinder, with the rotating speed ball milling 60min of high energy ball mill with 400 commentaries on classics/min, promptly get and flood required powder suspension.
(3) dipping powder suspension to three-dimensional porous electrolyte skeleton: be placed on three-dimensional porous electrolyte skeleton on 60 ℃ of heating plates; Then the powder hanging drop is added in the stephanoporate framework; Treat that solvent evaporates finishes, be placed on 450 ℃ of roasting 30min in the Muffle furnace, it is inferior to repeat this step 3.
(4) high temperature sintering: the electrode that obtains step 3 obtains three-dimensional composite cathode at 1000 ℃ of following sintering 120min, and this composite cathode has nucleocapsid structure, and promptly nuclear is the electrolyte skeleton, and shell is the phase reaction layer of stabilized nano membrane structure.The mass fraction of nano thin-film=nano thin-film quality/(nano thin-film quality+stephanoporate framework quality)=30% wherein.
Fig. 2 is the sketch map according to the three-dimensional composite cathode with nucleocapsid structure of the inventive method preparation; Its center and electrolyte are commaterial, and the composite cathode of therefore preparing has similar thermal coefficient of expansion with electrolyte, makes battery have good thermo-mechanical robust performance, and skeleton and electrolyte matrix are connected firmly and play transmission O
2-Effect; Shell is the phase reaction layer of stabilized nano membrane structure, and this phase reaction layer has the electronic and ionic mixed conductivity, and it is active to have higher hydrogen reduction.
Embodiment 2: preparation is with Sm
0.2Ce
0.8O
1.9Electrolyte is a stephanoporate framework, Co (NO
3)
3And Sr (NO
3)
3Solution is the composite cathode of maceration extract.
Step is following:
(1) the three-dimensional porous electrolyte skeleton of preparation: with electrolyte Sm
0.2Ce
0.8O
1.9Do stephanoporate framework, the making step of skeleton is with embodiment 1, and difference is that the firing temperature of skeleton in the present embodiment is 1300 ℃/5h, obtains the three-dimensional porous electrolyte skeleton of thick 15 μ m porositys 45%.
(2) dipping of preparation cathode material composition is used nitrate solution: with Sr (NO
3)
3And Co (NO
3)
26H
2O is that 1:1 is mixed in the deionized water according to the mol ratio of metal ion Sr and Co, and the mol ratio according to total metal ion and glycine is the amount adding glycine of 1:2 then, with deionized water solution concentration is transferred to 1mol/L at last.Add before using nitrate solution and ethanol volume ratio as the ethanol of 3:1 as surfactant.
(3) dipping nitrate solution to three-dimensional porous electrolyte skeleton: be placed into three-dimensional porous electrolyte skeleton on 60 ℃ of heating plates; Be added drop-wise to nitrate solution in the stephanoporate framework then; After treating that solvent evaporates finishes, place it in 500 ℃ of roasting 60min in the Muffle furnace, it is inferior to repeat this step 4.
(4) high temperature sintering: the electrode that obtains step 3 obtains three-dimensional composite cathode at 1000 ℃ of following sintering 120min; This composite cathode has nucleocapsid structure; Promptly nuclear is the electrolyte skeleton; Shell is the phase reaction layer of stabilized nano membrane structure, wherein the mass fraction of nano thin-film=nano thin-film quality/(nano thin-film quality+stephanoporate framework quality)=25%.The phase reaction layer of stabilized nano membrane structure is that material and the phase reaction of stephanoporate framework generation solid phase behind the dipping generates, and has promptly both contained the element of maceration extract in this layer, contains the element in the stephanoporate framework again.
Resulting composite cathode microscopic appearance is as shown in Figure 3 in the present embodiment, is impregnated into intraskeletal Co (NO
3)
3And Sr (NO
3)
3With Sm
0.2Ce
0.8O
1.9Skeleton combines together, forms the phase reaction layer of membrane structure equably.Electrochemical results shows that prepared battery performance is superior among this embodiment, and stability is splendid.As shown in Figure 4, under 700 ℃ of middle temperature, the polarization resistance of negative electrode has only 0.07 Ω cm
2As shown in Figure 5, battery performance behind operation 200h under 700 ℃ is not seen decay.Explain that the cathode performance that the inventive method makes is superior, good stability is worthy to be popularized.
Embodiment 3: preparation is with BaZr
0.1Ce
0.7Y
0.2O
3-δElectrolyte is a stephanoporate framework, Co (NO
3)
3Solution is the composite cathode of maceration extract.
Step is following:
(1) the three-dimensional porous electrolyte skeleton of preparation: with electrolyte BaZr
0.1Ce
0.7Y
0.2O
3-δDo stephanoporate framework, Sm among the making step of skeleton and the embodiment 1 in the present embodiment
0.2Ce
0.8O
1.9The making step of skeleton is identical.The firing temperature of skeleton is 1400 ℃/4h in the present embodiment, obtains the three-dimensional porous electrolyte skeleton of thick 30 μ m porositys 40%.
(2) dipping of preparation cathode material composition is used nitrate solution: with Co (NO
3)
26H
2O joins in the deionized water, adds a certain amount of glycine then, and the mol ratio that makes Co metal ion and glycine is 1:2, with deionized water the concentration of solution is adjusted to 2mol/L.The volume ratio that adds nitrate solution and ethanol before using as the ethanol of 4:1 as surfactant.
(3) dipping Co (NO
3)
26H
2O solution to three-dimensional porous electrolyte skeleton: be placed into three-dimensional porous electrolyte skeleton on 60 ℃ of heating plates, then Co (NO
3)
26H
2The O drips of solution is added in the stephanoporate framework, treat that solvent evaporates finishes after, place it in 600 ℃ of roasting 30min in the Muffle furnace, repeat this step 5 time.
(4) high temperature sintering: the electrode that obtains step 3 obtains three-dimensional composite cathode at 1200 ℃ of following sintering 300min; This composite cathode has nucleocapsid structure; Promptly nuclear is the electrolyte skeleton; Shell is the phase reaction layer of stabilized nano membrane structure, wherein the mass fraction of nano thin-film=nano thin-film quality/(nano thin-film quality+stephanoporate framework quality)=45%.The phase reaction layer of stabilized nano membrane structure is that material and the phase reaction of stephanoporate framework generation solid phase behind the dipping generates, and has promptly both contained the element of maceration extract in this layer, contains the element in the stephanoporate framework again.
Fig. 6 is BaZr
0.1Ce
0.7Y
0.2O
3-δElectrolyte is a stephanoporate framework, Co (NO
3)
3Solution is the microscopic appearance figure of the composite cathode of maceration extract.As can be seen from the figure, be impregnated into Co (NO in the skeleton
3)
3And BaZr
0.1Ce
0.7Y
0.2O
3-δSkeleton is sintered to one, forms the phase reaction film of nanometerization comparatively uniformly, and is satisfactory for result; In addition, resulting composite cathode still keeps enough porositys (25%), to guarantee carrying out smoothly of mass transport process.
Embodiment 4: preparation is with electrolyte Gd
0.1Ce
0.9O
1.95Be stephanoporate framework, PrCoO
3Powder suspension is the composite cathode of maceration extract.
Step is following:
(1) the three-dimensional porous electrolyte skeleton of preparation: with electrolyte Gd
0.1Ce
0.9O
1.95Do stephanoporate framework, Sm among carcasing step in the present embodiment and the embodiment 1
0.2Ce
0.8O
1.9Skeleton identical.The skeleton firing temperature is 1300 ℃/8h, obtains the three-dimensional porous electrolyte skeleton of thick 10 μ m porositys 40%.
(2) the powder suspension of preparation cathode material: cathode powder PrCoO
3Adopt conventional sol-gel process synthetic, with identical among the embodiment 1.With 1g PrCoO
3Powder, 12ml ethylene glycol, 2ml polyvinyl alcohol and 1g citric acid are put into ball grinder, with the rotating speed ball milling 60min of high energy ball mill with 400 commentaries on classics/min, promptly get and flood required powder suspension.
(3) dipping powder suspension to three-dimensional porous electrolyte skeleton: be placed on three-dimensional porous electrolyte skeleton on 60 ℃ of heating plates; Then the powder hanging drop is added in the stephanoporate framework; Treat that solvent evaporates finishes, be placed on 500 ℃ of roasting 30min in the Muffle furnace, it is inferior to repeat this step 3.
(4) high temperature sintering: the electrode that obtains step 3 obtains three-dimensional composite cathode at 1100 ℃ of following sintering 30min, and this composite cathode has nucleocapsid structure, and promptly nuclear is the electrolyte skeleton, and shell is the phase reaction layer of stabilized nano membrane structure.The mass fraction of nano thin-film=nano thin-film quality/(nano thin-film quality+stephanoporate framework quality)=40% wherein.
The prepared composite negative electrode is made up of (by cathode material PrCoO the phase reaction layer of electrolyte skeleton and one deck stabilized nano membrane structure in the present embodiment
3With electrolyte Gd
0.1Ce
0.9O
1.95The solid phase phase reaction takes place to be generated); Have good thermomechanical property (because the thermal coefficient of expansion of this composite cathode and electrolyte matrix is very approaching) with respect to common composite cathode; Have superior thermal stability (because this nano thin-film is highly stable with respect to the nano particle of high surface energy) with respect to common impregnated electrode, it all has benefited from special nucleocapsid structure of the present invention.
Embodiment 5: preparation is with Sm
0.2Ce
0.8O
1.9Electrolyte is a stephanoporate framework, Ba (NO
3)
3, Co (NO
3)
3And Sr (NO
3)
3Solution is the composite cathode of maceration extract.
Step is following:
(1) the three-dimensional porous electrolyte skeleton of preparation: with electrolyte Sm
0.2Ce
0.8O
1.9Do stephanoporate framework, the making step of skeleton is identical with embodiment 1, and difference is that the firing temperature of skeleton in the present embodiment is 1350 ℃/5h, obtains the three-dimensional porous electrolyte skeleton of thick 20 μ m porositys 40%.
(2) dipping of preparation cathode material composition is used nitrate solution: with Ba (NO
3)
3, Sr (NO
3)
3And Co (NO
3)
26H
2O is that 1:0.5:2 is mixed in the deionized water according to the mol ratio of metal ion Ba, Sr and Co, and the mol ratio according to total metal ion and glycine is the amount adding glycine of 1:3 then, with deionized water solution concentration is transferred to 0.5mol/L at last.Add before using nitrate solution and ethanol volume ratio as the ethanol of 3:1 as surfactant.
(3) dipping nitrate solution to three-dimensional porous electrolyte skeleton: be placed into three-dimensional porous electrolyte skeleton on 60 ℃ of heating plates; Be added drop-wise to nitrate solution in the stephanoporate framework then; After treating that solvent evaporates finishes, place it in 500 ℃ of roasting 60min in the Muffle furnace, it is inferior to repeat this step 4.
(4) high temperature sintering: the electrode that obtains step 3 obtains three-dimensional composite cathode at 1000 ℃ of following sintering 120min; This composite cathode has nucleocapsid structure; Promptly nuclear is the electrolyte skeleton; Shell is the phase reaction layer of stabilized nano membrane structure, wherein the mass fraction of nano thin-film=nano thin-film quality/(nano thin-film quality+stephanoporate framework quality)=25%.The phase reaction layer of stabilized nano membrane structure is that material and the phase reaction of stephanoporate framework generation solid phase behind the dipping generates, and has promptly both contained the element of maceration extract in this layer, contains the element in the stephanoporate framework again.
The prepared composite negative electrode is made up of (by nitrate Ba (NO the phase reaction layer of electrolyte skeleton and one deck stabilized nano membrane structure in the present embodiment
3)
3, Sr (NO
3)
3And Co (NO
3)
26H
2O and electrolyte Sm
0.2Ce
0.8O
1.9The solid phase phase reaction takes place to be generated); Have good thermomechanical property (because the thermal coefficient of expansion of this composite cathode and electrolyte matrix is very approaching) with respect to common composite cathode; Have superior thermal stability (because this nano thin-film is highly stable with respect to the nano particle of high surface energy) with respect to common impregnated electrode, it all has benefited from special nucleocapsid structure of the present invention.
Embodiment 6: preparation is with BaZr
0.8Y
0.2O
3-δElectrolyte is a stephanoporate framework, Co (NO
3)
3Solution is the composite cathode of maceration extract.
Step is following:
(1) the three-dimensional porous electrolyte skeleton of preparation: with electrolyte BaZr
0.8Y
0.2O
3-δDo stephanoporate framework, Sm among the making step of skeleton and the embodiment 1 in the present embodiment
0.2Ce
0.8O
1.9The making step of skeleton is identical.The firing temperature of skeleton is 1400 ℃/5h in the present embodiment, obtains the three-dimensional porous electrolyte skeleton of thick 20 μ m porositys 40%.
(2) dipping of preparation cathode material composition is used nitrate solution: with Co (NO
3)
26H
2O joins in the deionized water, adds a certain amount of glycine then, and the mol ratio that makes Co metal ion and glycine is 1:2, with deionized water the concentration of solution is adjusted to 1.5mol/L.The volume ratio that adds nitrate solution and ethanol before using as the ethanol of 4:1 as surfactant.
(3) dipping Co (NO
3)
26H
2O solution to three-dimensional porous electrolyte skeleton: be placed into three-dimensional porous electrolyte skeleton on 60 ℃ of heating plates, then Co (NO
3)
26H
2The O drips of solution is added in the stephanoporate framework, treat that solvent evaporates finishes after, place it in 600 ℃ of roasting 30min in the Muffle furnace, repeat this step 5 time.
(4) high temperature sintering: the electrode that obtains step 3 obtains three-dimensional composite cathode at 1200 ℃ of following sintering 300min; This composite cathode has nucleocapsid structure; Promptly nuclear is the electrolyte skeleton; Shell is the phase reaction layer of stabilized nano membrane structure, wherein the mass fraction of nano thin-film=nano thin-film quality/(nano thin-film quality+stephanoporate framework quality)=40%.The phase reaction layer of stabilized nano membrane structure is that material and the phase reaction of stephanoporate framework generation solid phase behind the dipping generates, and has promptly both contained the element of maceration extract in this layer, contains the element in the stephanoporate framework again.
The prepared composite negative electrode is made up of (by the nitrate Co (NO of dipping the phase reaction layer of electrolyte skeleton and one deck stabilized nano membrane structure in the present embodiment
3)
26H
2O and electrolyte BaZr
0.8Y
0.2O
3-δThe solid phase phase reaction takes place to be generated); Have good thermomechanical property (because the thermal coefficient of expansion of this composite cathode and electrolyte matrix is very approaching) with respect to common composite cathode; Have superior thermal stability (because this nano thin-film is highly stable with respect to the nano particle of high surface energy) with respect to common impregnated electrode, it all has benefited from special nucleocapsid structure of the present invention.
Claims (10)
1. compound cathode of solid oxide fuel battery, it is characterized in that: composite cathode has nucleocapsid structure, and its center is the electrolyte skeleton, and shell is the phase reaction layer of stabilized nano membrane structure, and the mass fraction that shell accounts for whole composite cathode is 25%-45%; The phase reaction layer is that cathode material and the phase reaction of skeleton generation solid phase behind the dipping generates, and has both contained the element in the maceration extract in this layer, contains the element in the skeleton again.
2. a kind of compound cathode of solid oxide fuel battery according to claim 1 is characterized in that the electrolyte skeleton has three-dimensional porous structure, and porosity is 30% ~ 60%; The thickness of electrolyte skeleton is 10 ~ 30 μ m; Described electrolyte skeleton is the skeleton that oxygen ion conductor oxide and/or proton conductor oxide are formed.
3. a kind of compound cathode of solid oxide fuel battery according to claim 1 is characterized in that the oxygen ion conductor oxide is a kind of in doping of cerium oxide oxygen ion conductor oxide, stable zirconium oxide-oxygen ion conductor oxide, lanthanum gallium based perovskite type oxygen ion conductor oxide or the aluminium base Ca-Ti ore type oxygen ion conductor of the lanthanum oxide; The proton conductor oxide is a kind of in the sub-conductor oxide of strontium cerium matrix, the sub-conductor oxide of strontium zirconium matrix, the sub-conductor oxide of barium cerium matrix or the sub-conductor oxide of barium zirconium matrix.
4. method for preparing compound cathode of solid oxide fuel battery as claimed in claim 1, its concrete steps are following: one, high temperature sintering prepares the three-dimensional porous skeleton that electrolyte is formed; Two, the powder suspension or the presoma nitrate solution of preparation cathode material; Three, powder suspension that obtains in the step 2 or nitrate solution are impregnated in the stephanoporate framework that obtains in the step 1, then at 400 ~ 600 ℃ of roasting 30 ~ 60min; Four, repeating step three reaches required pickup; Five, 1000-1200 ℃ of high temperature sintering 30 ~ 300min under the air atmosphere promptly obtains having the three-dimensional composite cathode of nucleocapsid structure.
5. method according to claim 4 is characterized in that the temperature that high temperature sintering in the step 1 prepares three-dimensional porous skeleton is 1250 ~ 1400 ℃, and sintering time is 4 ~ 8h.
6. method according to claim 4; The powder suspension that it is characterized in that cathode material in the step 2 is the suspension that mixes through the powder after sol-gel process, solid phase method, the hydrothermal synthesis method preparation and dispersant, organic solvent and surfactant; Wherein said powder is Ln
xCo
2-xO
y, Ln=Y wherein, La, Pr, Nd, Sm, Gd or Dy, Sr
xCo
2-xO
y, Ba
xCo
2-xO
y, Co
3O
4, Co
2O
3Or one or more of CoO, 1>=x>0,3>=y>2; Described organic solvent is ethanol, ethylene glycol, 1, one or more in 2-butanediol or the acetone; Wherein the usage ratio of powder and organic solvent is 80 ~ 120g/L; Described dispersant is polyethylene glycol or polyvinyl alcohol, and wherein dispersant is 1 ~ 3:10 with the volume of organic solvent ratio; Described surfactant is one or more in citric acid, ethylenediamine tetra-acetic acid, urea, glycine or the triethanolamine, and wherein the quality of surfactant is 1 ~ 2 times of powder quality.
7. method according to claim 6 is characterized in that described powder is SrCoO
3, Co
3O
4
8. method according to claim 4, the presoma nitrate solution that it is characterized in that cathode material in the step 2 is the mixed aqueous solution of nitrate, complexing agent and surfactant; Wherein the concentration of presoma nitrate solution is 0.1 ~ 2mol/L; Described nitrate is Co (NO
3)
3, or Ln (NO
3)
3, Sr (NO
3)
3Or Ba (NO
3)
3In one or more and Co (NO
3)
3Mixing, Ln=Y wherein, La, Pr, Nd, Sm, Gd or Dy; Described complexing agent is one or more in citric acid, ethylenediamine tetra-acetic acid, urea or the glycine, and wherein the consumption of complexing agent is 1 ~ 3 times of amount of substance of total metal ion; Described surfactant is an ethanol, and wherein the volume ratio of nitrate solution and ethanol is 1 ~ 4.
9. method according to claim 4 is characterized in that described nitrate is Co (NO
3)
3, or Co (NO
3)
3And Sr (NO
3)
3The mol ratio of metal ion be 1: mix (0.5 ~ 1.5).
10. method according to claim 4, the number of operations that it is characterized in that described repeating step three is 3 ~ 5 times.
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Application publication date: 20120919 |