CN105734607A - High temperature solid oxide electrolytic bath with double-layer composite interlayer - Google Patents
High temperature solid oxide electrolytic bath with double-layer composite interlayer Download PDFInfo
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- CN105734607A CN105734607A CN201410742472.4A CN201410742472A CN105734607A CN 105734607 A CN105734607 A CN 105734607A CN 201410742472 A CN201410742472 A CN 201410742472A CN 105734607 A CN105734607 A CN 105734607A
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Abstract
The invention relates to a high temperature solid oxide electrolytic bath with a double-layer composite interlayer. The high temperature solid oxide electrolytic bath is characterized in that the double-layer composite interlayer with thickness of 1-10 microns is arranged between an electrolytic bath anode and an electrolyte, a layer of the double-layer composite interlayer close to the electrolyte comprises a rare-earth metal oxide, a layer of the double-layer composite interlayer close to the anode comprises a transition metal oxide, and the double-layer composite interlayer can catch elements which easily diffuse and react in the anode and react with the caught elements to produce a novel catalytic activity substance so that electrolyte erosion caused by the easily diffused and reacted elements is reduced and chemical compatibility between the anode and the electrolyte of the electrolytic bath is improved. The anode/electrolyte interface resistance of the double-layer composite interlayer is very small so that the double-layer composite interlayer has high stability.
Description
Technical field
The present invention relates to a kind of high-temperature solid oxide electrolyzer with two-layer compound interlayer, it is characterized in that introducing between anode and electrolyte the geocomposite layer that rare earth is constituted with transition metal oxide, thus improving the chemical compatibility of high-temperature solid oxide electrolytic cell anode/electrolyte interface.
Background technology
High-temperature solid oxide electrolyzer is the electrolysis installation that one operates in middle high temperature (600～800 DEG C), has benefited from its higher operating temperature, it is possible to steam electrolysis prepares hydrogen and oxygen efficiently.Existing solid oxide fuel cell system is substantially continued to use in the design of current electrolytic tank of solid oxide, its Typical Disposition adopts the zirconic composite cermet material (Ni-YSZ) of metallic nickel and stabilized with yttrium oxide to make negative electrode, electrolyte made by the zirconium oxide (YSZ) of stabilized with yttrium oxide, and perofskite type oxide makes anode.Wherein the rate constants of the overall electrolytic efficiency of decision is the oxygen evolution reaction of anode, therefore to realize efficient electrolysis, uses the La of high catalytic activity1-xSrxCo1-yFeyO3-δOr Ba1-xSrxCo1-yFeyO3-δIt it is essential condition.But, when this kind of high activity Ca-Ti ore type anode material directly contacts with Zirconia electrolytic, Sr element therein is easy to form SrZrO with Zr3This kind of high resistance material, affects battery performance and life-span.Traditional solution is that the cerium oxide (GDC) with Gd2 O3 does intermediate layer isolation containing Sr electrode and containing Zr electrolyte, the method can delay the diffusion of Sr, but the consistency requirements in GDC intermediate layer is significantly high, it is necessary to use the technology such as physical vapour deposition (PVD), cause that preparation cost rises.Therefore, isolate beyond Sr element using the GDC mode as passive protection, in addition it is also necessary to introduce some new elements thereon and carry out function modified so that it is possess the conversion that actively reacts with Sr, and form the effect of active substance once again, thus improving the stability of electrode/electrolyte interface.
Summary of the invention
For overcoming existing high-temperature solid oxide electrolyzer to use the La containing Sr1-xSrxCo1-yFeyO3-δOr Ba1-xSrxCo1-yFeyO3-δHigh performance anode easily reacts generation high resistance material SrZrO with the YSZ containing Zr3Problem, the invention provides a kind of high-temperature solid oxide electrolyzer with two-layer compound interlayer.
This invention address that the scheme that its technical problem adopts is:
A kind of high-temperature solid oxide electrolyzer with two-layer compound interlayer, described electrolyzer is made up of cathode layer, dielectric substrate, two-layer compound interlayer, anode layer, two-layer compound interlayer is between anode layer and dielectric substrate, in two-layer compound interlayer, close electrolytical one layer is rare-earth oxide, one layer of close anode is transition metal oxide, two-layer compound interlayer can catch the element of easily diffusion in anode, and form new catalytic active substance with the element reaction easily spread, easily spread element to electrolytical erosion thus reducing.
Middle rare earth metal-oxide of the present invention is one or two or more kinds composition in the oxide of Ce, Sm, Gd；Described transition metal oxide is one or two or more kinds composition in Ti, Fe, Co, Cu.
In the two-layer compound interlayer of the present invention, transition metal oxide proportion is 10%～80%.
In the present invention, the thickness of two-layer compound interlayer is 1～10 micron, it is preferable that thickness is 1～5 micron.
In the present invention, dielectric substrate is the zirconium oxide (YSZ) of stabilized with yttrium oxide；Anode layer is La1-xSrxCo1-yFeyO3-δOr Ba1-xSrxCo1-yFeyO3-δThe perovskite material of (0 < x < 1,0 < y < 1 ,-0.10≤δ≤0.5) type.
In the present invention, the concrete preparation method of two-layer compound interlayer is as follows:
(1) with the nitrate corresponding to transition metal oxide, rare-earth oxide required in geocomposite layer being configured to solution in proportion, after precipitating with sodium carbonate liquor titration, aging, sucking filtration also dries；
(2) by after broken for gained depositing abrasive, in 500～800 DEG C of heat treatments 2～6 hours；
(3) gained powder is scattered in n-butyl alcohol and PVA system, and mixes 30～60 hours with ultrasonic vibration；
(4) being arranged on rotary coating device by coin electrolyzer substrate, control rotating speed is 500～3000rpm；
(5) take dispersion liquid, according to required geocomposite layer thickness, correspondingly drip 1～10 on electrolyte；
(6) by the electrolyzer substrate after coating after drying at room temperature, roasting 1～10 hour at 500～1200 DEG C, after roasting, rare-earth oxide and transition metal oxide are divided into upper and lower two-layer automatically；
(7) anode slurry is coated with on decorative layer after baking, roasting 1～10 hour at 500～1500 DEG C, namely obtain the high-temperature solid oxide electrolyzer with two-layer compound interlayer of the present invention.
The invention has the beneficial effects as follows, described geocomposite layer can catch the element of easy diffusion reaction in anode, and reacts the catalytic active substance that formation is new, thus reducing it to electrolytical erosion.Anode/electrolyte interface after the method is improved has less resistance, and electrolyzer presents higher stability.
Accompanying drawing explanation
Fig. 1 changes the change that cell operation performance is caused by transition metal oxide ratio in geocomposite layer.
Fig. 2 is the cross section structure schematic diagram of the electrolyzer with two-layer compound interlayer.
Detailed description of the invention
Embodiment 1
Select Co3O4With GDC compound
(1) by Co (NO3)2With Ce (NO3)3、Gd(NO3)3Being configured to solution by metal ion molar ratio 10:8:2, after precipitating with 1M sodium carbonate liquor titration, aging, sucking filtration also dries；
(2) by after broken for gained depositing abrasive, in 500 DEG C of heat treatments 2 hours；
(3) gained powder is scattered in n-butyl alcohol and (according to 1:40 ratio) in PVA system, and mixes 30 hours with ultrasonic vibration；
(4) being arranged on rotary coating device by coin electrolyzer substrate, control rotating speed is 3000rpm；
(5) take dispersion liquid, according to required thickness, correspondingly drip 2 on electrolyte；
(6) by the electrolyzer substrate after coating after drying at room temperature, roasting 2 hours at 500 DEG C；
(7) by La0.6Sr0.4Co0.2Fe0.8O3-δOn anode slurry coating decorative layer after baking, roasting 2 hours at 1000 DEG C, namely obtain the high-temperature solid oxide electrolyzer with functional geocomposite layer of the present invention.
Embodiment 2
Electrochemical property test: by above-mentioned containing Co3O4GDC complex function interlayer electrolytic tank of solid oxide be arranged on chemical property valuator device and test.Controlling negative electrode atmosphere is 50%H2-50%H2O, flow 200ml/min, anode atmosphere is 100%O2, flow 100ml/min.Fig. 1 is the Co that two-layer compound interlayer contains different quality ratio3O4Electrolyzer polarization curve under above-mentioned operating mode.Containing Co3O4Higher electrolyzer performance is also higher, and when testing temperature and being 800 DEG C, the lower electric current density of 0.2V bias can reach 550mA/cm2, be equivalent to often produce 1 cubic metre of hydrogen consumption and be about 3kWh electric energy.
Embodiment 3
Select Fe3O4With GDC compound
(1) by Fe (NO3)3With Ce (NO3)3、Gd(NO3)3Being configured to solution by metal ion molar ratio 10:8:2, after precipitating with 1M sodium carbonate liquor titration, aging, sucking filtration also dries；
(2) by after broken for gained depositing abrasive, in 500 DEG C of heat treatments 2 hours；
(3) gained powder is scattered in n-butyl alcohol and (according to 1:40 ratio) in PVA system, and mixes 30 hours with ultrasonic vibration；
(4) being arranged on rotary coating device by coin electrolyzer substrate, control rotating speed is 3000rpm；
(5) take dispersion liquid, according to required thickness, correspondingly drip 2 on electrolyte；
(6) by the electrolyzer substrate after coating after drying at room temperature, roasting 2 hours at 500 DEG C；
(7) by Ba0.5Sr0.5Co0.2Fe0.8O3-δOn anode slurry coating decorative layer after baking, roasting 2 hours at 1000 DEG C, namely obtain the high-temperature solid oxide electrolyzer with functional geocomposite layer of the present invention.
Embodiment 4
Electrochemical property test: by above-mentioned containing Fe3O4GDC complex function interlayer electrolytic tank of solid oxide be arranged on chemical property valuator device and test.Controlling negative electrode atmosphere is 50%H2-50%H2O, flow 200ml/min, anode atmosphere is 100%O2, flow 100ml/min.Fe in two-layer compound interlayer3O4Mass ratio when being 50%, when testing temperature and being 800 DEG C, under 0.2V bias, the electric current density of electrolyzer can reach 500mA/cm2。
Claims (6)
1. a high-temperature solid oxide electrolyzer with two-layer compound interlayer, it is characterized in that: described electrolyzer is overlapped successively constituted by cathode layer, dielectric substrate, two-layer compound interlayer, anode layer, two-layer compound interlayer is between anode layer and dielectric substrate, in two-layer compound interlayer, close electrolytical one layer is rare-earth oxide layer, and one layer of close anode is transition metal oxide layer.
2. the high-temperature solid oxide electrolyzer with two-layer compound interlayer according to claim 1, it is characterised in that: described rare-earth oxide is one or two or more kinds composition in the oxide of Ce, Sm or Gd；Described transition metal oxide is one or two or more kinds composition in Ti, Fe, Co or Cu.
3. the high-temperature solid oxide electrolyzer with two-layer compound interlayer according to claim 1, it is characterized in that: described rare-earth oxide is with the two-layer compound interlayer of transition metal oxide composition, and mass ratio shared by transition metal oxide is 10%～80%.
4. the high-temperature solid oxide electrolyzer with two-layer compound interlayer according to claim 1, it is characterised in that: the thickness of described two-layer compound interlayer is 1～10 micron, it is preferable that thickness is 1～5 micron.
5. the high-temperature solid oxide electrolyzer with two-layer compound interlayer according to claim 1, it is characterised in that: described dielectric substrate is the zirconium oxide (YSZ) of stabilized with yttrium oxide；Described anode layer is La1-xSrxCo1-yFeyO3-δOr Ba1-xSrxCo1-yFeyO3-δThe perovskite material of (0 < x < 1,0 < y < 1,0≤δ≤0.5) type.
6. the high-temperature solid oxide electrolyzer with two-layer compound interlayer according to claim 1, it is characterized in that: two-layer compound interlayer can catch the element of easily diffusion in anode, and form new catalytic active substance with the element reaction easily spread, easily spread element to electrolytical erosion thus reducing.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106884182A (en) * | 2017-03-22 | 2017-06-23 | 成都艾欧新能源科技有限公司 | High-temperature solid oxide electrolytic cell |
| CN114561656A (en) * | 2022-04-06 | 2022-05-31 | 北京理工大学 | Medium-low temperature metal support solid oxide electrolytic cell |
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| CN114561656A (en) * | 2022-04-06 | 2022-05-31 | 北京理工大学 | Medium-low temperature metal support solid oxide electrolytic cell |
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