CN105734607B - A kind of high-temperature solid oxide electrolytic cell with two-layer compound interlayer - Google Patents
A kind of high-temperature solid oxide electrolytic cell with two-layer compound interlayer Download PDFInfo
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- CN105734607B CN105734607B CN201410742472.4A CN201410742472A CN105734607B CN 105734607 B CN105734607 B CN 105734607B CN 201410742472 A CN201410742472 A CN 201410742472A CN 105734607 B CN105734607 B CN 105734607B
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Abstract
The present invention relates to a kind of high-temperature solid oxide electrolytic cells with two-layer compound interlayer, it is characterised in that：A kind of two-layer compound interlayer with a thickness of 1~10 micron is introduced between the anode and electrolyte of electrolytic cell, it is rare-earth oxide close to one layer of electrolyte, one layer close to electrode is transition metal oxide, the geocomposite layer can capture the element of easy diffusion reaction in anode, and it reacts with it and to form new catalytic active substance, to reduce erosion of the element to electrolyte of easy diffusion reaction, chemical compatibility between electrolytic cell anode and electrolyte is improved.The anode/electrolyte interface resistance of electrolytic cell with two-layer compound interlayer is very small, and electrolytic cell shows higher stability.
Description
Technical field
The present invention relates to a kind of high-temperature solid oxide electrolytic cells with two-layer compound interlayer, it is characterized in that anode with
The geocomposite layer that rare earth and transition metal oxide are constituted is introduced between electrolyte, to improve high-temperature solid oxide electrolysis
The chemical compatibility at pond anode/electrolyte interface.
Background technique
High-temperature solid oxide electrolytic cell is the electrolysis installation that one kind operates in high temperature (600~800 DEG C), has benefited from it
Vapor can efficiently be electrolysed and hydrogen and oxygen is made by higher operating temperature.Electrolytic tank of solid oxide is set at present
Meter substantially continues to use existing solid oxide fuel cell system, and Typical Disposition uses the oxygen of metallic nickel and stabilized with yttrium oxide
The composite cermet material (Ni-YSZ) for changing zirconium makees cathode, and the zirconium oxide (YSZ) of stabilized with yttrium oxide makees electrolyte, Ca-Ti ore type
Oxide makees anode.The rate constants for wherein determining whole electrolytic efficiency are the oxygen evolution reactions of anode, therefore in order to realize efficiently
Electrolysis, uses the La of high catalytic activity1-xSrxCo1-yFeyO3-δOr Ba1-xSrxCo1-yFeyO3-δIt is necessary condition.However, this kind of
When high activity Ca-Ti ore type anode material is directly in contact with Zirconia electrolytic, Sr element therein is easy to be formed with Zr
SrZrO3This kind of high resistance substance, influences battery performance and service life.Traditional solution is the cerium oxide (GDC) with Gd2 O3
The diffusion of Sr can be delayed by making middle layer isolation electrode containing Sr and electrolyte containing Zr, this method, but to the compactness of GDC middle layer
It is required that it is very high, it needs to cause preparation cost soaring using technologies such as physical vapour deposition (PVD)s.Therefore, GDC is being used to prevent as passive
The mode of shield is isolated other than Sr element, it is also necessary to be introduced some new elements on it and be carried out function modified, have it actively
It reacts conversion with Sr, and forms the effect of active material once again, to improve the stability of electrode/electrolyte interface.
Summary of the invention
To overcome existing high-temperature solid oxide electrolytic cell to use the La containing Sr1-xSrxCo1-yFeyO3-δOr Ba1-xSrxCo1- yFeyO3-δHigh performance anode, which is easily reacted with the YSZ containing Zr, generates high resistance substance SrZrO3The problem of, the present invention provides one kind
High-temperature solid oxide electrolytic cell with two-layer compound interlayer.
The present invention solves scheme used by its technical problem：
A kind of high-temperature solid oxide electrolytic cell with two-layer compound interlayer, the electrolytic cell is by cathode layer, electrolyte
Layer, two-layer compound interlayer, anode layer are constituted, and two-layer compound interlayer is between anode layer and electrolyte layer, two-layer compound interlayer
In close to one layer of electrolyte be rare-earth oxide, one layer close to anode is transition metal oxide, two-layer compound every
Layer can capture the element easily spread in anode, and form new catalytic active substance with the element reaction easily spread, to reduce
Easily erosion of the diffusion element to electrolyte.
Rare-earth oxide is one of oxide of Ce, Sm, Gd or two kinds of composition described above in the present invention；Described
Transition metal oxide is one of Ti, Fe, Co, Cu or two kinds of composition described above.
In two-layer compound interlayer of the invention, transition metal oxide proportion is 10%~80%.
In the present invention two-layer compound interlayer with a thickness of 1~10 micron, preferred thickness is 1~5 micron.
Electrolyte layer is the zirconium oxide (YSZ) of stabilized with yttrium oxide in the present invention；Anode layer is La1-xSrxCo1-yFeyO3-δOr
Ba1-xSrxCo1-yFeyO3-δ(0<x<1,0<y<1, -0.10≤δ≤0.5) type perovskite material.
The specific preparation method of two-layer compound interlayer is as follows in the present invention：
(1) by nitrate corresponding to rare-earth oxide needed for geocomposite layer and transition metal oxide press than
Example is configured to solution, after sodium carbonate liquor titration precipitating, aging, suction filtration and drying；
(2) it after being crushed gained depositing abrasive, is heat-treated 2~6 hours in 500~800 DEG C；
(3) it disperses gained powder in n-butanol and PVA system, and with ultrasonic vibration mixing 30~60 hours；
(4) coin electrolytic cell substrate is mounted on rotary coating device, control revolving speed is 500~3000rpm；
(5) dispersion liquid is taken, according to required geocomposite layer thickness, correspondingly drips 1~10 drop on electrolyte；
(6) it by the electrolytic cell substrate after coating after drying at room temperature, roasts 1~10 hour, roasts at 500~1200 DEG C
Rare-earth oxide and transition metal oxide are divided into upper layer and lower layer automatically afterwards；
(7) anode slurry is coated on decorative layer after baking, roasts 1~10 hour, that is, obtains at 500~1500 DEG C
Obtain the high-temperature solid oxide electrolytic cell of the present invention with two-layer compound interlayer.
The invention has the advantages that the geocomposite layer can capture the element of easy diffusion reaction in anode, and and its
Reaction forms new catalytic active substance, to reduce its erosion to electrolyte.Through the improved anode/electrolyte of this method
Interface has smaller resistance, and electrolytic cell shows higher stability.
Detailed description of the invention
Fig. 1 is to change ratio of the transition metal oxide in geocomposite layer to change caused by cell operation performance.
Fig. 2 is the cross section structure schematic diagram of the electrolytic cell with two-layer compound interlayer.
Specific embodiment
Embodiment 1
Select Co3O4It is compound with GDC
(1) by Co (NO3)2With Ce (NO3)3、Gd(NO3)3By metal ion molar ratio example 10:8:2 are configured to solution, with 1M
After sodium carbonate liquor titration precipitating, aging, suction filtration and drying；
(2) it after being crushed gained depositing abrasive, is heat-treated 2 hours in 500 DEG C；
(3) it disperses gained powder in n-butanol and PVA system (according to 1:40 ratios), and with ultrasonic vibration mixing 30
Hour；
(4) coin electrolytic cell substrate is mounted on rotary coating device, control revolving speed is 3000rpm；
(5) dispersion liquid is taken, according to required thickness, correspondingly drips 2 drops on electrolyte；
(6) it by the electrolytic cell substrate after coating after drying at room temperature, is roasted 2 hours at 500 DEG C；
(7) by La0.6Sr0.4Co0.2Fe0.8O3-δOn the decorative layer of anode slurry coating after baking, roasted at 1000 DEG C
2 hours, that is, obtain the high-temperature solid oxide electrolytic cell with functional geocomposite layer of the present invention.
Embodiment 2
Electrochemical property test：Contain Co for above-mentioned3O4GDC complex function interlayer electrolytic tank of solid oxide be mounted on
It is tested on chemical property valuator device.Control cathode atmosphere is 50%H2- 50%H2O, flow 200ml/min, anode gas
Atmosphere is 100%O2, flow 100ml/min.Fig. 1 is the Co that two-layer compound interlayer contains different quality ratio3O4Electrolytic cell above-mentioned
Polarization curve under operating condition.Containing Co3O4Higher electrolytic cell performance is also higher, when test temperature is 800 DEG C, under 0.2V bias
Current density can reach 550mA/cm2, it is equivalent to and often produces 1 cubic metre of hydrogen consumption about 3kWh electric energy.
Embodiment 3
Select Fe3O4It is compound with GDC
(1) by Fe (NO3)3With Ce (NO3)3、Gd(NO3)3By metal ion molar ratio example 10:8:2 are configured to solution, with 1M
After sodium carbonate liquor titration precipitating, aging, suction filtration and drying；
(2) it after being crushed gained depositing abrasive, is heat-treated 2 hours in 500 DEG C；
(3) it disperses gained powder in n-butanol and PVA system (according to 1:40 ratios), and with ultrasonic vibration mixing 30
Hour；
(4) coin electrolytic cell substrate is mounted on rotary coating device, control revolving speed is 3000rpm；
(5) dispersion liquid is taken, according to required thickness, correspondingly drips 2 drops on electrolyte；
(6) it by the electrolytic cell substrate after coating after drying at room temperature, is roasted 2 hours at 500 DEG C；
(7) by Ba0.5Sr0.5Co0.2Fe0.8O3-δOn the decorative layer of anode slurry coating after baking, roasted at 1000 DEG C
2 hours, that is, obtain the high-temperature solid oxide electrolytic cell with functional geocomposite layer of the present invention.
Embodiment 4
Electrochemical property test：Contain Fe for above-mentioned3O4GDC complex function interlayer electrolytic tank of solid oxide be mounted on
It is tested on chemical property valuator device.Control cathode atmosphere is 50%H2- 50%H2O, flow 200ml/min, anode gas
Atmosphere is 100%O2, flow 100ml/min.Fe in two-layer compound interlayer3O4Mass ratio be 50% when, when test temperature be 800
DEG C when, under 0.2V bias, the current density of electrolytic cell can reach 500mA/cm2。
Claims (7)
1. a kind of high-temperature solid oxide electrolytic cell with two-layer compound interlayer, it is characterised in that：The electrolytic cell is by cathode
Layer, electrolyte layer, two-layer compound interlayer, anode layer successively overlap composition, and two-layer compound interlayer is located at anode layer and electrolyte layer
Between, one layer in two-layer compound interlayer close to electrolyte layer is rare-earth oxide layer, and one layer close to anode layer was
Cross metal oxide layer.
2. the high-temperature solid oxide electrolytic cell with two-layer compound interlayer according to claim 1, it is characterised in that：
The rare-earth oxide is one of oxide of Ce, Sm or Gd or two kinds of composition described above；The transition gold
Belonging to oxide is one of Ti, Fe, Co or Cu or two kinds of composition described above.
3. the high-temperature solid oxide electrolytic cell with two-layer compound interlayer according to claim 1, it is characterised in that：
In the two-layer compound interlayer of the rare-earth oxide and transition metal oxide composition, quality shared by transition metal oxide
Than being 10% ~ 80%.
4. the high-temperature solid oxide electrolytic cell with two-layer compound interlayer according to claim 1, it is characterised in that：
The two-layer compound interlayer with a thickness of 1 ~ 10 micron.
5. with the high-temperature solid oxide electrolytic cell of two-layer compound interlayer according to claim 4, it is characterised in that：
The two-layer compound interlayer with a thickness of 1 ~ 5 micron.
6. the high-temperature solid oxide electrolytic cell with two-layer compound interlayer according to claim 1, it is characterised in that：
The electrolyte layer is the zirconium oxide of stabilized with yttrium oxide（YSZ）；The anode layer is La1-xSrxCo1-yFeyO3-δ, wherein 0<x<
1,0<y<1,0≤δ≤0.5 or Ba1-xSrxCo1-yFeyO3-δ, wherein 0<x<1,0<y<The perovskite material of the type of 1,0≤δ≤0.5
Material.
7. the high-temperature solid oxide electrolytic cell with two-layer compound interlayer according to claim 1, it is characterised in that：
Two-layer compound interlayer can capture the element easily spread in anode, and new catalytic activity object is formed with the element reaction easily spread
Matter, to reduce easily erosion of the diffusion element to electrolyte.
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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 |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5106706A (en) * | 1990-10-18 | 1992-04-21 | Westinghouse Electric Corp. | Oxide modified air electrode surface for high temperature electrochemical cells |
| US6228521B1 (en) * | 1998-12-08 | 2001-05-08 | The University Of Utah Research Foundation | High power density solid oxide fuel cell having a graded anode |
| CN1553538A (en) * | 2003-06-06 | 2004-12-08 | 中国科学院过程工程研究所 | Intermediate temperature solid oxide fuel battery material combing system |
| CN1747212A (en) * | 2005-10-11 | 2006-03-15 | 厦门大学 | Structure of fuel battery electrode/sandwich/electrolyte from solid oxide |
| CN1783554A (en) * | 2004-12-02 | 2006-06-07 | 中国科学院大连化学物理研究所 | Film electrode structure of solid oxide fuel cell and preparing method |
| CN101304093A (en) * | 2007-05-11 | 2008-11-12 | 中国科学院大连化学物理研究所 | Low temperature solid-oxide fuel battery three-in-one component MEA and preparation thereof |
| CN101304092A (en) * | 2007-05-11 | 2008-11-12 | 中国科学院大连化学物理研究所 | Cathode material of mid-temperature solid-oxide fuel battery and uses thereof |
| CN103361671A (en) * | 2012-03-26 | 2013-10-23 | 株式会社东芝 | Solid oxide electrochemical cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014060028A (en) * | 2012-09-18 | 2014-04-03 | Toyota Motor Corp | Solid oxide fuel battery |
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- 2014-12-08 CN CN201410742472.4A patent/CN105734607B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5106706A (en) * | 1990-10-18 | 1992-04-21 | Westinghouse Electric Corp. | Oxide modified air electrode surface for high temperature electrochemical cells |
| US6228521B1 (en) * | 1998-12-08 | 2001-05-08 | The University Of Utah Research Foundation | High power density solid oxide fuel cell having a graded anode |
| CN1553538A (en) * | 2003-06-06 | 2004-12-08 | 中国科学院过程工程研究所 | Intermediate temperature solid oxide fuel battery material combing system |
| CN1783554A (en) * | 2004-12-02 | 2006-06-07 | 中国科学院大连化学物理研究所 | Film electrode structure of solid oxide fuel cell and preparing method |
| CN1747212A (en) * | 2005-10-11 | 2006-03-15 | 厦门大学 | Structure of fuel battery electrode/sandwich/electrolyte from solid oxide |
| CN101304093A (en) * | 2007-05-11 | 2008-11-12 | 中国科学院大连化学物理研究所 | Low temperature solid-oxide fuel battery three-in-one component MEA and preparation thereof |
| CN101304092A (en) * | 2007-05-11 | 2008-11-12 | 中国科学院大连化学物理研究所 | Cathode material of mid-temperature solid-oxide fuel battery and uses thereof |
| CN103361671A (en) * | 2012-03-26 | 2013-10-23 | 株式会社东芝 | Solid oxide electrochemical cell |
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