CN109913900A - It is a kind of to be used for CO with high catalytic activity2The SOEC cathode material of electrolysis - Google Patents
It is a kind of to be used for CO with high catalytic activity2The SOEC cathode material of electrolysis Download PDFInfo
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- CN109913900A CN109913900A CN201910311843.6A CN201910311843A CN109913900A CN 109913900 A CN109913900 A CN 109913900A CN 201910311843 A CN201910311843 A CN 201910311843A CN 109913900 A CN109913900 A CN 109913900A
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Abstract
The present invention relates to a kind of to be used for CO with high catalytic activity2The SOEC cathode material of electrolysis, belongs to clean energy technology field.The purpose of the present invention is be directed to existing cathode of electrolytic tank of solid oxide material for CO2Adsorption capacity is poor, and catalytic activity is low, to provide a kind of cathode of electrolytic tank of solid oxide material with high absorption capacity and catalytic activity the problem of influencing battery electrolysis performance and conversion ratio；The cathode material passes through the dual regulation of perovskite oxide non-stoichiometric and doped chemical, A omission and B doping Mo elements, is conducive to raising conductivity to guarantee enough active sites and improves material to CO2Catalytic activity change the electronic structure of material entirety and the energy of system, improve material to CO while in B doping Cu elements2Adsorption capacity, realize improve electrolytic tank of solid oxide electrolysis performance and stability purpose.
Description
Technical field
The present invention relates to a kind of to be used for CO with high catalytic activity2Electrolytic tank of solid oxide (SOEC) cathode of electrolysis
Material belongs to clean energy technology field.
Background technique
Due to being depended on unduly to fossil fuel, the excess emissions of carbon dioxide are caused, a series of environment is resulted in
Problem, in recent years, people are dedicated to how reducing the discharge of carbon dioxide and effective trans-utilization to carbon dioxide, solid
Oxidate electrolytic cell is a kind of very promising energy technology, has high conversion, greenhouse gases can be converted into fuel
Gas.Global Greenhouse Effect can not only be alleviated, moreover it is possible to reduce dependence of the mankind to fossil fuel.
Traditional cathode material of electrolytic tank of solid oxide is nickel based metal Ceramic Composite electrode at present, but it is in high temperature
Under the conditions of be easy sintering lead to cell performance decay, another question is to CO2Catalytic activity is poor, this is because CO2It is straight
Linear molecule lacks polarity, makes electrode material to CO2Adsorption capacity it is very poor, it is more difficult to carry out further electrochemical reaction, lead
The more difficult promotion of conversion ratio is caused, the electrolysis performance of battery is poor, and uses noble metal catalyst higher cost.
Existing patent of invention (106498435 B of Publication No. CN) proposes a kind of cathode material in electrolytic process not
Protection of reducing atmosphere is needed, and still maintains stable in high decomposition voltage flowering structure, but there is no solve cathode material to two
The problem of carbonoxide adsorptivity difference.
Summary of the invention
The purpose of the present invention is be directed to existing cathode of electrolytic tank of solid oxide material for CO2Adsorption capacity is poor, catalysis
Activity is low, to provide a kind of couple of CO the problem of influencing battery electrolysis performance and conversion ratio2It lives with high absorption capacity and catalysis
The cathode of electrolytic tank of solid oxide material of property；The cathode material passes through perovskite oxide non-stoichiometric and doped chemical
Dual regulation, A is vacant and B doping Mo elements, is conducive to raising conductivity and mentions to guarantee enough active sites
High material is to CO2Catalytic activity change the electronic structure of material entirety and the energy of system while in B doping Cu elements,
Material is improved to CO2Adsorption capacity, realize improve electrolytic tank of solid oxide electrolysis performance and stability purpose.
The purpose of the present invention is what is be achieved through the following technical solutions.
It is a kind of to be used for CO with high catalytic activity2The cathode of electrolytic tank of solid oxide material of electrolysis, molecular formula are
SrxTi0.9-yCuyMo0.1O3-δ(STCM), the Sr content x numerical value is 0.95-1, and the Cu content y numerical value is 0.1-0.4.
The preparation method of the STCM cathode material include: method of electrostatic spinning, solid phase method, combustion method, sol-gel method,
Hydro-thermal method or solvent-thermal method.
The method that the STCM cathode material is prepared using sol-gel method, specific steps are as follows: by metal salt and citric acid
It is added to the water and for water-bath heating stirring to gel state, drying obtains presoma at 150~250 DEG C, then will at 60~90 DEG C
Presoma 900~1200 DEG C of 5~10h of roasting under air atmosphere obtain STCM cathode material；
The molar ratio of metal ion is 1.5~2:1 in the citric acid and metal salt；The metal salt includes strontium salt, titanium
Salt, mantoquita and molybdenum salt, wherein the molar ratio of the metal ion of strontium salt, titanium salt, mantoquita and molybdenum salt is 0.95~1:0.8~0.5:
0.1~0.4:0.1.
The strontium salt includes strontium nitrate, strontium acetate or strontium oxalate.
The mantoquita includes copper nitrate, copper acetate or cupric oxalate.
The titanium salt is butyl titanate.
The molybdenum salt is ammonium molybdate.
Prepare electrolytic tank of solid oxide as cathode material using above-mentioned STCM: the STCM cathode material passes through silk screen
The method of printing is coated on La0.9Sr0.1Ga0.8Mg0.2O3-δOn electrolyte, and with commercialized La0.6Sr0.4Co0.2Fe0.8O3
(LSCF) single battery is made as anode material, the CO of 50ml/min is passed through to cathode side2, anode-side exposure is in air.
The cathode coating thickness is 10~30 μm.
Beneficial effect
It is disclosed by the invention it is a kind of with high catalytic activity be used for CO2The cathode of electrolytic tank of solid oxide material of electrolysis
Material, as new material SrxTi0.9-yCuyMo0.1O3-δ(STCM), cathode material of the STCM as electrolytic tank of solid oxide,
There is high stability in the cathode atmosphere of electrolytic tank of solid oxide, and regulated and controled by the doping of Cu, improve material to CO2
Absorption, catalytic activity, the single battery of preparation realizes higher current density and good output stability, at 800 DEG C
Operating temperature under maximum current density can achieve 2.09A/cm2, under 750 DEG C of operating temperatures can with steady operation 110h with
On.
Detailed description of the invention
Fig. 1 is the XRD diagram of the STCM cathode material with high stability and catalytic activity；
Fig. 2 is the battery discharge curve figure of example 1 group dress；
Fig. 3 is the battery CO of example 1 group dress2Conversion ratio figure；
Fig. 4 is the CO of material2- TPD curve；
Fig. 5 is the battery discharge curve figure that embodiment 2 assembles.
Specific embodiment
The invention will be further described with embodiment with reference to the accompanying drawing.
Embodiment 1
It is a kind of to be used for CO with high catalytic activity2The cathode of electrolytic tank of solid oxide material of electrolysis, specific molecular formula
For Sr0.975Ti0.7Cu0.2Mo0.1O3-δ。
The preparation method is as follows:
Take 2.063g strontium nitrate, 2.3793g butyl titanate, 0.4832g Gerhardite, 0.1766g ammonium molybdate is molten
In 500ml deionized water, 8.3g citric acid, 80 DEG C of heating water bath stirrings, until green transparent gel is formed, 250 are added
Drying obtains brown presoma at DEG C, by 1000 DEG C of roasting 5h are obtained with perovskite under air atmosphere after presoma grinding carefully
The Sr of phase structure0.975Ti0.7Cu0.2Mo0.1O3-δ, as shown in Figure 1, XRD analysis shows that prepared oxide corresponds to perovskite
Base peak.
Using the material of synthesis as cathode material, La0.6Sr0.4Co0.2Fe0.8O3It (LSCF) is anode material,
La0.9Sr0.1Ga0.8Mg0.2O3-δ(LSGM) it is used as electrolyte, by electrode material brush in electrolyte two by way of silk-screen printing
Side is assembled into single battery, electrode layer with a thickness of 25 μm, with the CO of 50ml/min2It is passed through in cathode chamber, anode is in static state
Air atmosphere, the maximum current density that battery is realized at 800 DEG C of operating temperature are 2.516A/cm2.As shown in Figure 2.Battery exists
800 DEG C of operating temperature, when application voltage is 1.6v, CO2The conversion ratio for being converted into CO reaches 65%, as shown in Figure 3.
CO is carried out to the cathode material of synthesis2- TPD test, method particularly includes: weigh the cathode material powder of 150mg synthesis
Body is down to room temperature after 300 DEG C of pre-burning 30min under helium atmosphere, then be passed through CO carefully after grinding uniformly2, by two hours
Adsorption process after switch to helium atmosphere, by adsorption instrument temperature programming to 1000 DEG C, carry out CO2- TPD test, and record
CO2Desorption curve, as shown in figure 4, occurring CO after 800 DEG C2Desorption peaks illustrate material at 700-800 DEG C of SOEC operating temperature
There is good CO2Adsorption activity.
Embodiment 2
It is a kind of to be used for CO with high catalytic activity2The cathode of electrolytic tank of solid oxide material of electrolysis, specific molecular formula
For SrTi0.7Cu0.2Mo0.1O3-δ。
The preparation method is as follows:
Take 2.1163g strontium nitrate, 2.3793g butyl titanate, 0.4832g Gerhardite, 0.1766g ammonium molybdate,
It is dissolved in 500ml deionized water, 8.4056g citric acid, 80 DEG C of heating water bath stirrings is added, until green transparent gel is formed,
Drying obtains brown presoma at 250 DEG C, by 1000 DEG C of roasting 5h are had under air atmosphere after presoma grinding carefully
The SrTi of Perovskite Phase structure0.7Cu0.2Mo0.1O3-δ, as shown in Figure 1, XRD analysis shows that prepared oxide corresponds to perovskite
Base peak.
Using the material of preparation as cathode material, with La0.6Sr0.4Co0.2Fe0.8O3It (LSCF) is anode material, with
La0.9Sr0.1Ga0.8Mg0.2O3-δ(LSGM) it is used as electrolyte, by electrode material brush in electrolyte two by way of silk-screen printing
Side is assembled into single battery, electrode layer with a thickness of 25 μm, with the CO of 50ml/min2It is passed through in cathode chamber, anode is in static state
Air atmosphere, the maximum current density that battery is realized at 800 DEG C of operating temperature are 1.75A/cm2, as shown in Figure 5.
Using the CO of the cathode material of the method test synthesis in embodiment 12- TPD, 800 DEG C there is CO later2Desorption peaks,
Illustrate that material has good CO at 700-800 DEG C of SOEC operating temperature2Adsorption activity.
Embodiment 3
It is a kind of to be used for CO with high catalytic activity2The cathode of electrolytic tank of solid oxide material of electrolysis, specific molecular formula
For Sr0.975Ti0.6Cu0.3Mo0.1O3-δ, using Solid phase synthesis material, it is specific the preparation method is as follows:
Weigh 2.879g strontium carbonate, 0.9588g titanium dioxide, 0.4773g copper oxide, 0.2879g molybdenum oxide is placed in ball milling
In machine for 24 hours with the speed ball milling of 400 revolution per seconds, by the powder after ball milling, 1100 DEG C of roasting 10h are had under air atmosphere
The Sr of Perovskite Phase structure0.975Ti0.6Cu0.3Mo0.1O3-δCathode material.
Using the material of preparation as cathode material, with La0.6Sr0.4Co0.2Fe0.8O3It (LSCF) is anode material, with
La0.9Sr0.1Ga0.8Mg0.2O3-δ(LSGM) be used as electrolyte, electrode layer with a thickness of 20 μm, with the CO of 50ml/min2It is passed through yin
In pole room, anode is in still air atmosphere, and battery operating temperature is 800 DEG C, and the maximum current density of realization is 2.09A/
cm2。
Embodiment 4
It is a kind of to be used for CO with high catalytic activity2The cathode of electrolytic tank of solid oxide material of electrolysis, specific molecular formula
For SrTi0.5Cu0.4Mo0.1O3-δ, using Solid phase synthesis material, it is specific the preparation method is as follows:
Weigh 2.9526g strontium carbonate, 0.799g titanium dioxide, 0.6364g copper oxide, 0.2879g molybdenum oxide is placed in ball milling
In machine for 24 hours with the speed ball milling of 400 revolution per seconds, by the powder after ball milling, 1100 DEG C of roasting 10h are had under air atmosphere
The SrTi of Perovskite Phase structure0.5Cu0.4Mo0.1O3-δCathode material.
Using the material of preparation as cathode material, with La0.6Sr0.4Co0.2Fe0.8O3It (LSCF) is anode material, with
La0.9Sr0.1Ga0.8Mg0.2O3-δ(LSGM) be used as electrolyte, electrode layer with a thickness of 20 μm, with the CO of 50ml/min2It is passed through yin
In pole room, anode is in still air atmosphere, and battery operating temperature is 800 DEG C, and the maximum current density of realization is 1.5A/cm2。
Above-described specific descriptions have carried out further specifically the purpose of invention, technical scheme and beneficial effects
It is bright, it should be understood that the above is only a specific embodiment of the present invention, the protection model being not intended to limit the present invention
It encloses, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should be included in the present invention
Protection scope within.
Claims (6)
1. a kind of be used for CO with high catalytic activity2The SOEC cathode material of electrolysis, it is characterised in that: molecular formula is
SrxTi0.9-yCuyMo0.1O3-δ, the Sr content x numerical value is 0.95-1, and the Cu content y numerical value is 0.1-0.4.
2. the method for preparing cathode material as described in claim 1, it is characterised in that: include: method of electrostatic spinning, solid phase method, combustion
Burning method, sol-gel method, hydro-thermal method or solvent-thermal method.
3. the method for preparing cathode material as described in claim 1 using sol-gel method, it is characterised in that: specific steps are as follows:
Metal salt and citric acid are added to the water and water-bath heating stirring is dried at 150~250 DEG C to gel state at 60~90 DEG C
Presoma is obtained, then 900~1200 DEG C of roasting 5h obtain STCM cathode material under air atmosphere by presoma；The citric acid
Molar ratio with metal ion in metal salt is 1.5~2:1；The metal salt includes strontium salt, titanium salt, mantoquita and molybdenum salt, wherein
Strontium salt, titanium salt, mantoquita and molybdenum salt the molar ratio of metal ion be 0.95~1:0.8~0.5:0.1~0.4:0.1.
4. method as claimed in claim 3, it is characterised in that: the strontium salt includes strontium nitrate, strontium acetate or strontium oxalate；The copper
Salt includes copper nitrate, copper acetate or cupric oxalate；The titanium salt includes butyl titanate；The molybdenum salt includes ammonium molybdate.
5. the method for preparing electrolytic tank of solid oxide using cathode material as described in claim 1, it is characterised in that: described
STCM cathode material is coated on La by the method for silk-screen printing0.9Sr0.1Ga0.8Mg0.2O3-δOn electrolyte, and with
La0.6Sr0.4Co0.2Fe0.8O3Single battery is made as anode material, the CO of 50ml/min is passed through to cathode side2, anode-side is sudden and violent
Dew is in air.
6. method as claimed in claim 5, it is characterised in that: the cathode coating thickness is 10~30 μm.
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| JP4821217B2 (en) * | 2005-08-31 | 2011-11-24 | ソニー株式会社 | Positive electrode active material, positive electrode and battery |
| US20130228716A1 (en) * | 2011-08-31 | 2013-09-05 | Kabushiki Kaisha Toshiba | Magnetic material, method for producing magnetic material, and inductor element |
| CN104900887A (en) * | 2015-06-14 | 2015-09-09 | 吉林大学 | Double-perovskite type intermediate temperature solid oxide fuel cell anode material and preparation method |
| CN108048955A (en) * | 2017-12-07 | 2018-05-18 | 北京理工大学 | The preparation method of strontium iron molybdenum base double-perovskite type metal oxide nanofibres |
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2019
- 2019-04-18 CN CN201910311843.6A patent/CN109913900A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1035324A (en) * | 1988-02-21 | 1989-09-06 | 中国科学院物理研究所 | No rare earth high-temperature superconductor Alloy And Preparation Method |
| CN1315920A (en) * | 1998-07-16 | 2001-10-03 | 拉瓦勒大学 | Process for synthesizing metal oxides and metal oxide having perovskite or perovskite-like crystal structure |
| CN1672284A (en) * | 2002-08-01 | 2005-09-21 | 圣安德鲁斯大学董事会 | Perovskite-based fuel cell electrode and membrane |
| JP4821217B2 (en) * | 2005-08-31 | 2011-11-24 | ソニー株式会社 | Positive electrode active material, positive electrode and battery |
| US20130228716A1 (en) * | 2011-08-31 | 2013-09-05 | Kabushiki Kaisha Toshiba | Magnetic material, method for producing magnetic material, and inductor element |
| CN104900887A (en) * | 2015-06-14 | 2015-09-09 | 吉林大学 | Double-perovskite type intermediate temperature solid oxide fuel cell anode material and preparation method |
| CN108048955A (en) * | 2017-12-07 | 2018-05-18 | 北京理工大学 | The preparation method of strontium iron molybdenum base double-perovskite type metal oxide nanofibres |
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Application publication date: 20190621 |