CN104934613B - A kind of high-temperature solid oxide electrolytic cell anode material and composite anode materials - Google Patents
A kind of high-temperature solid oxide electrolytic cell anode material and composite anode materials Download PDFInfo
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- CN104934613B CN104934613B CN201410100878.2A CN201410100878A CN104934613B CN 104934613 B CN104934613 B CN 104934613B CN 201410100878 A CN201410100878 A CN 201410100878A CN 104934613 B CN104934613 B CN 104934613B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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- 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
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Abstract
The present invention relates to high-temperature solid oxide electrolytic cell anode material, it is characterised in that：The anode material is spinel oxides, or spinelle is with having the composite that the oxide of oxygen-ion conduction forms.The high-temperature solid oxide electrolyte anode has good catalytic activity and stability.
Description
Technical field
The present invention relates to the anode material of high-temperature solid oxide electrolytic cell, it is characterized in that using spinel oxides,
Or the composite that spinelle forms with the oxide with oxygen-ion conduction does anode.
Background technology
High-temperature solid oxide electrolytic cell is that one kind operates in high temperature（600~800 DEG C）Electrolysis installation, have benefited from it
Higher operating temperature, efficiently vapor can be electrolysed and hydrogen and oxygen is made.Electrolytic tank of solid oxide is set at present
Meter substantially continues to use existing solid oxide fuel cell system, and its Typical Disposition is using metallic nickel and the oxygen of stabilized with yttrium oxide
Change the composite cermet material of zirconium（Ni-YSZ cermet）Make hydrogen electrode, the zirconium oxide of stabilized with yttrium oxide（YSZ）It is electrolysed
Matter, perofskite type oxide（Such as La0.8Sr0.2MnO3+δ、La0.6Sr0.4Co0.2Fe0.8O3-δDeng）Make oxygen electrode.Wherein determine overall
The rate constants of electrolytic efficiency are the Oxygen anodic evolution reactions on oxygen electrode, therefore the catalytic activity for improving anode is to realize efficient electric
The necessary condition of solution.However, when the Ca-Ti ore type oxygen electrode used in conventional solid oxide fuel cells is directly used in electrolysis,
Present the defects of certain.La0.8Sr0.2MnO3+δThe most significant problem of-YSZ combination electrodes is the appearance that worked under electrolysis mode
Electrode delamination easily occurs, this is due to La0.8Sr0.2MnO3+δ- YSZ reactivity is relatively low, is acted in additional polarization current
Under, oxygen separates out and destroys the linkage interface of electrode-electric solution matter by force.La0.6Sr0.4Co0.2Fe0.8O3-δBecause with electronics-
Ar ion mixing conductance, reactivity is higher, and the phenomenon of electrode delamination will not occur substantially, but performance is shown during longtime running
Decay is very fast, less stable.Its main cause is that the presence of Co elements can improve electro catalytic activity, but also makes A bits simultaneously
Plain LaIt is easier to Sr from electrode to electrolyte diffusion, forms the high resistant phases such as zirconic acid lanthanum, strontium zirconate.Therefore, using without La or
The electrode material of Sr elements is to improve electrolytic cell stability and a kind of feasible method in life-span.
Spinel oxides are widely used in the stainless steel connector surface of high temperature solid oxide fuel cell/electrolytic cell
Coating, its formula are (A, B)3O4, when A, B are transiting group metal elements, the spinel-like generally has good electronic conductance
With the thermal coefficient of expansion for matching other battery components（J.Am.Ceram.Soc.,90[5]1515-1520(2007)）, it may have one
Fixed electrocatalytic reaction activity（Int.J.Hydrogen Energy,381052-1057(2013)）.Due to this spinel-like not
Containing the alkaline earths such as La or Sr or rare earth element, therefore there is good chemical compatibility with electrolyte.Therefore, it is as high-temperature electrolysis pond
Anode both can guarantee that electro catalytic activity, can also reach higher stability.
The content of the invention
To overcome the shortcomings of that existing high-temperature solid oxide electrolytic cell anode catalytic activity or less stable, the present invention carry
Supply a kind of to have high catalytic activity and the new type high temperature solid oxide electrolytic cell anode of high stability concurrently.
Scheme is used by the present invention solves its technical problem：Anode material uses spinel oxides, or point crystalline substance
The composite that stone forms with the oxide with oxygen-ion conduction.
The chemical formula of spinel oxides of the present invention is (A, B)3O4, wherein A and B are Li, B, Mg, Al, Si,
K、Ca、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Ge、Y、Zr、Nb、Mo、Tc、Ru、Rh、Pd、Ag、Sn、Ba、La、
One or more in Ce, Pr, Nd, Sm, Gd, W, Ir, Pt, Au, Bi.
(A, B) of the present invention3O4Element A in type spinel oxides, preferably be selected from Li, Mg, K, Ca, Ti, Cr, Fe,
One or more in Ni, Zn, Ga, Y, Zr, Nb, Mo, Ru, Ba, La, Ce, Pr, Nd, Sm, Gd, W, Bi.
(A, B) of the present invention3O4B element in type spinel oxides, preferably be selected from B, Al, Si, Sc, V, Mn, Ni,
One or more in Cu, Ge, Tc, Rh, Pd, Ag, Sn, Ir.
High-temperature solid oxide electrolytic cell anode material of the present invention can adapt to zirconia series electrolyte, or oxygen
Change cerium series electrolyte, or lanthanum gallate series of electrolyte.
Composite anode of the present invention is by (A, B)3O4Type spinel oxide and another oxygen with oxygen-ion conduction
Compound mixes, and wherein the mass fraction of oxygen ion conductor is 10%~90%.
Oxide of the present invention with oxygen-ion conduction for doping zirconium oxide system oxide, or doping oxidation
Cerium system oxide, or the gallic acid lanthanide oxide of doping.
Spinel oxides of the present invention can be synthesized by combustion method, or coprecipitation, or solid reaction process.
The specific preparation method of high-temperature solid oxide electrolytic cell anode of the present invention is as follows：
（1）Using the nitrate corresponding to the cation for the spinel oxide to be synthesized as initiation material, by combustion method,
Or coprecipitation, or the spinelle needed for solid reaction process synthesis；
（2）The spinel powder of gained is ground, glue is added and is configured to ink-like slurry；
（3）When needing to prepare spinelle with oxygen ion conductor powder and mixing the composite of composition, then by required oxygen
Ion conductor powder grinding, ink-like slurry is configured to after well mixed according in 1~99% ratio incorporation spinel powder；
（4）One or more oxides needed for modified coatings are configured to slurry according to required concentration, coated in electrolysis
Matter surface, it is calcined 1~100 hour at 500~1500 DEG C；
（5）On anode slurry coating decorative layer after baking, 1~100 hour will be calcined at 500~1500 DEG C, i.e.,
Obtain the high-temperature solid oxide electrolytic cell of the present invention with Novel anode.
The invention has the advantages that described high-temperature solid oxide electrolytic cell anode has higher catalytic activity, with
The good compatibility of other battery components, while also can guarantee that the stability of longtime running.
Brief description of the drawings
Fig. 1 is (A, B)3O4Type spinelle anode is distinguished from top to bottom in the cross-sectional scans electron microscope being electrolysed after testing, figure
For electrolyte, decorative layer, spinelle anode；
Fig. 2 is the polarization curve using the electrolytic cell of spinelle anode；
Fig. 3 is the stability test result using the electrolytic cell of spinelle anode.
Embodiment
Following examples will be further described to the present invention, but not thereby limiting the invention.
Embodiment 1
Combustion method prepares CoAl2O4The specific steps of type spinel powder：
Take the AB of stoichiometric proportion（Co and Al）The nitrate of element, addition EDTA and ammonium citrate, wherein metal ion,
EDTA, the molar ratio of ammonium citrate are 1:1:1.5, dissolve by heating in deionized water, treat the water evaporation in solution, to system
After jelly, being heated at 500 DEG C makes colloid that self-propagating combustion occur, and organic matter therein is removed, and obtains just powder.Then will
It is calcined 1 hour at 900 DEG C, obtains required spinel powder.
Coprecipitation prepares CoAl2O4The specific steps of type spinel powder：
1.5mol/L ammonium bicarbonate soln is prepared, pH value is adjusted to 11.5 with ammoniacal liquor.Take the AB of stoichiometric proportion（Co and
Al）Solution is made in the nitrate of element, is heating and is being added drop-wise to dropwise in above-mentioned ammonium bicarbonate soln under stirring condition, it is heavy to be formed
Form sediment.Precipitation aging filters after 24 hours, washs, dries and grind, and is then calcined 10 hours at 900 DEG C, obtains required point
Spar powder.
Solid reaction process prepares ZnMn2O4The specific steps of type spinel powder：
Take the AB of stoichiometric proportion（Zn and Mn）The nitrate mixing of element, using ethanol as medium, is dried after ball milling 24h,
And be calcined 50 hours at 1500 DEG C, obtain required spinel powder.
Embodiment 2
Combustion method as described in embodiment 1 prepares CoAl2O4Powder, the 1g powders are taken, add 0.94g terpinols, 0.06g
Ethyl cellulose is deployed into ink-like slurry, takes 0.01g CoAl2O4Electrode slurry is coated on electrolyte, at 800 DEG C after drying
Roasting 10 hours, that is, it is CoAl to obtain anode2O4Electrolytic tank of solid oxide.Fig. 1 is the cross-sectional scans electron microscope of electrolytic cell,
It is respectively electrolyte, spinelle anode from top to bottom in figure.
Embodiment 3
Combustion method as described in embodiment 1 prepares CoAl2O4Powder, the 0.5g powders are taken, 0.5gYSZ powder is added, in second
Ground and mixed is uniformly and after drying in alcohol, adds 0.94g terpinols, 0.06g ethyl celluloses are deployed into the compound sun of ink-like
Pole slurry, take 0.01g CoAl2O4Electrode slurry is calcined 5 hours coated on electrolyte after drying at 800 DEG C.Afterwards compound
0.02g CoAl are coated with anode2O4As current collector layer, it is calcined 2 hours at 700 DEG C after drying, that is, obtains CoAl2O4- YSZ is multiple
The electrolytic tank of solid oxide of Heyang pole.
Embodiment 4
Electrochemical property test：CoAl will be contained described in embodiment 32O4The Ni-YSZ/YSZ/ of spinelle anode
CoAl2O4Electrolytic tank of solid oxide is arranged on chemical property valuator device and tested.It is 50%H to control negative electrode atmosphere2-
50%H2O, flow 200ml/min, anode atmosphere 100%O2, flow 100ml/min.When test temperature is 800 DEG C, electricity is hankered
Pressure current density can reach 500mA/cm2, equivalent to often producing 1 cubic metre of hydrogen consumption 3.11kWh electric energy.Fig. 2 is the electricity
Polarization curves of the Xie Chi under above-mentioned operating mode.
Embodiment 5
ZnMn prepared by the solid reaction process described in embodiment 12O4, take the 1g powders, add 0.94g terpinols,
0.06g ethyl celluloses are deployed into ink-like slurry, take 0.01gZnMn2O4Electrode slurry coated on electrolyte, after drying
800 DEG C are calcined 2 hours, that is, it is ZnMn to obtain anode2O4Electrolytic tank of solid oxide.
Embodiment 6
Stability test：ZnMn will be contained described in embodiment 52O4The Ni-YSZ/YSZ/ZnMn of spinelle anode2O4Gu
Oxide body electrolytic cell is arranged on chemical property valuator device and tested.It is 50%H to control negative electrode atmosphere2-50%H2O, stream
Measure 200ml/min, anode atmosphere 100%O2, flow 100ml/min.When test temperature be 850 DEG C, the electric current of constant-current discharge
Density is 300mA/cm2When, voltage stabilization is maintained at 1.25V.Fig. 3 is that the electrolytic cell is steady under the conditions of above-mentioned constant-current discharge
Qualitative test result.
Claims (5)
1. a kind of high-temperature solid oxide electrolytic cell anode material is in high-temperature solid oxide electrolytic cell as anode material
Using, it is characterised in that：The anode material is spinel oxides, and its chemical formula is AXB3-XO4, 0 ＜ X ＜ 3；
Wherein element A be selected from Li, Mg, K, Ca, Ti, Cr, Fe, Co, Zn, Ga, Y, Zr, Nb, Mo, Ru, Ba, La, Ce, Pr, Nd,
One or two or more kinds in Sm, Gd, W, Bi；
Wherein one kind in B, Al, Si, Sc, V, Mn, Ni, Cu, Ge, Tc, Rh, Pd, Ag, Sn, Ir of B element or two kinds with
On.
2. application according to claim 1, it is characterised in that：The 0.1 ＜ X ＜ 2.9.
3. application according to claim 1, it is characterised in that：0.5 ＜ X ＜ 2.5 in the spinel oxides.
4. application according to claim 1, it is characterised in that：The anode material can adapt to zirconia series electrolysis
Matter, or cerium oxide series of electrolyte, or lanthanum gallate series of electrolyte.
5. a kind of composite anode containing anode material described in claim 1 is used as anode in high-temperature solid oxide electrolytic cell
The application of material, it is characterised in that：The composite anode is by AXB3-XO4Type spinel oxide has oxonium ion electricity with another
The oxide led mixes, wherein the mass fraction of the oxide with oxygen-ion conduction is 10% ~ 90%；
The oxide with oxygen-ion conduction in composite anode is the zirconium oxide system oxide of doping, or the cerium oxide of doping
Oxide, or the gallic acid lanthanide oxide of doping；
The zirconium oxide system oxide of described doping is doped with the one or two or more kinds in yittrium oxide, scandium oxide, cerium oxide
The mass content of the zirconium oxide of oxide, wherein zirconium oxide is 90% ~ 99%；
The cerium oxide oxide of the doping is doped with one or two or more kinds of oxygen in gadolinium oxide, samarium oxide, lanthana
The mass content of the cerium oxide of compound, wherein cerium oxide is 90% ~ 99%；
The gallic acid lanthanide oxide of the doping is the gallium doped with one or two or more kinds of oxides in strontium oxide strontia, magnesia
The mass content of sour lanthanum, wherein lanthanum gallate is 90% ~ 99%.
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| DE102016223414A1 (en) * | 2016-11-25 | 2018-05-30 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | An anode for an electrochemical cell and a method for producing an electrochemical cell with such an anode |
| CN107482226B (en) * | 2017-08-02 | 2019-11-26 | 周坤 | A kind of solid oxide fuel cell fuel electrode material and preparation method thereof |
| CN109286022B (en) * | 2018-09-27 | 2020-10-23 | 中国华能集团清洁能源技术研究院有限公司 | Manufacturing process of corrosion-resistant molten carbonate fuel cell bipolar plate material |
| CN111715235B (en) * | 2019-03-19 | 2021-06-15 | 中国科学院大连化学物理研究所 | High-temperature anti-loss ruthenium monatomic catalyst and preparation and application thereof |
| CN113443654B (en) * | 2021-07-16 | 2022-07-22 | 中国科学院兰州化学物理研究所 | Rare earth doped spinel material with electromagnetic wave regulation and control function and preparation thereof |
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| CN102340008A (en) * | 2010-07-22 | 2012-02-01 | 中国科学院大连化学物理研究所 | Cathode material of solid oxide fuel cell and preparation method thereof |
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| US20090011323A1 (en) * | 2007-07-05 | 2009-01-08 | General Electric Company | Solid Oxide Electrochemical Devices Having an Improved Electrode |
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