CN110336041A - A kind of ruthenium nickel combination electrode and its preparation method and application - Google Patents
A kind of ruthenium nickel combination electrode and its preparation method and application Download PDFInfo
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Abstract
A kind of solid oxide fuel cell electrode preparation technical field of the present invention, and in particular to ruthenium nickel combination electrode and its preparation method and application.This method includes in the precursor solution drop coating to nickel base electrode ontology by ruthenium, it is dried after standing, then after being successively fired, cooling down, the Ni-based combination electrode of ru oxide is made, it repeats the above steps until the content of ruthenium is 0.5-3wt% in nickel base electrode ontology, finally to treated, the Ni-based combination electrode of ru oxide is restored, and ruthenium nickel combination electrode is made, and the ammonolysis craft catalytic activity and electric conductivity of electrode made from this method are preferable；In addition, the electrode has preferable ammonolysis craft catalytic activity, more hydrogen can be provided for battery, ruthenium-based catalyst has preferable low temperature active, the low temperature electrochemical performance of battery is made to be improved.
Description
Technical field
SOFC electrode fabrication of the present invention field, and in particular to a kind of ruthenium nickel combination electrode and preparation method thereof and answer
With.
Background technique
The problems such as because of environmental pollution and greenhouse effects, the energy resource structure based on traditional carbonylation energy are faced with huge
Challenge, Hydrogen Energy because its cleaning, energy per mass density is high, from a wealth of sources the advantages that be considered as the following fossil fuel substitution
Performance source.Along with the gradually industrialization of hydrogen fuel cell technology, efficient, carbon-free utilize of Hydrogen Energy also be will be realized.Currently,
The big crucial problem of need to solve one is efficient, safe hydrogen storage technology.
Ammonia is not only important inorganic chemical product, also has unique advantage as hydrogen carrier.Ammonia is easy to liquefy, tool
Nonhazardous, hydrogen-storage density height, production storaging and transport technology are mature under irritant smell, non-combustible and low concentration, and hydrogen production process
Middle non-carbon-emitting is a kind of efficient, cleaning and safety hydrogen storage carrier.
Direct Ammonia Tubular Solid Oxide Fuel Cell (SOFC) can directly convert ammonia into stable electric energy, but due to tradition
SOFC anode uses nickel-base material, and the ammonia catalytic activity of base metal nickel at low temperature significantly reduces, and direct ammonia SOFC is caused to exist
Low temperature (600 DEG C) electrochemistry below can significantly reduce.Ruthenium ammonolysis craft low-temperature catalytic activity with higher and stability, but
Its ammonia catalytic activity and carrier, auxiliary agent and preparation method are closely related.
A kind of system of compound hydrogen-precipitating electrode of porous Ni-base ru oxide is disclosed in Chinese patent literature CN103422116A
Preparation Method first pre-processes nickel substrate, then porous Ni-base presoma electrode is prepared using the method for electro-deposition, in the electricity
The electrolyte of extremely upper deposition ruthenic chloride, amion acetic acid and sodium nitrate, so that porous Ni-base ru oxide combination electrode is prepared,
But the electrode does not activate ammonia and carries out targeted design；Direct ammonia SOFC anode is nickel and soild oxide ionic conductor material
Mixed cermet electrodes need to develop steady load and high ammonia catalytic activity that corresponding preparation method realizes ruthenium.
Summary of the invention
Therefore, the technical problem to be solved in the present invention is that the ammonia in direct ammonia SOFC electrode in the prior art is overcome to urge
Change poor activity, the defects of low temperature electrochemical performance is poor, to provide a kind of preparation method of compound preparing hydrogen by ammonia decomposition electrode of ruthenium nickel.
For this purpose, the present invention provides following technical schemes.
The present invention provides a kind of preparation methods of ruthenium nickel combination electrode, including,
(1) by the precursor solution drop coating of ruthenium to nickel base electrode ontology, after standing, drying；
(2) nickel base electrode ontology is successively roasted and is cooled down, the Ni-based combination electrode of ru oxide is made；
(3) weigh and calculate the content of ruthenium in the Ni-based combination electrode of the ru oxide, repeat step (1) and (2) up to
The content of ruthenium is 0.5-3wt% in the nickel base electrode ontology；
(4) to step (3), treated that the Ni-based combination electrode of ru oxide restores, and ruthenium nickel combination electrode is made.
The nickel base electrode ontology includes electrode slice and the electrolyte layer being arranged on, and the electrolyte layer includes the first material
Material and the second material, first material are barium based perovskite, oxidation zirconium base rare-earth oxide, cerium oxide base rare earth metal
One of oxide, lanthanum gallate based perovskite；Second material is nickel source；
The oxidation zirconium base rare-earth oxide is yttria-stabilized zirconia or scandium oxide-stabilizing zirconia；
The cerium oxide base rare-earth oxide is the cerium oxide of Gd2 O3 or the cerium oxide of strontium doping；
The barium based perovskite is zirconium doped yttrium barium cerate, zirconium yttrium ytterbium doping barium cerate or doped yttrium barium zirconate；
The lanthanum gallate based perovskite is the lanthanum gallate of zirconium, strontium and magnesium doping.
The mass ratio of first material and the second material is 3:7-6:4.
Presoma in the precursor solution of the ruthenium be in ruthenic chloride, nitric acid ruthenium, acetic acid ruthenium or acetylacetone,2,4-pentanedione ruthenium extremely
Few one kind；
The solvent of the precursor solution of the ruthenium is water or ethyl alcohol；The quality of presoma point in the precursor solution of the ruthenium
Number is 3-15%.
Further, the time of the standing is 0.5-1.5h；
The drying temperature is 80-120 DEG C, drying time 0.4-1.2h.
The temperature of the roasting is 400-500 DEG C, and the time of the roasting is 15-30min.
It further, further include with the heating rate of 1-1.5 DEG C/min by the nickel base electrode sheet before the roasting
The step of body is warming up to 400-500 DEG C.
The reduction is that treated that the Ni-based combination electrode of ru oxide is placed under atmosphere of hydrogen carries out by step (3),
The temperature of the reduction is 600-800 DEG C, time 0.5-2h.
The present invention also provides a kind of ruthenium nickel combination electrodes, are made using above-mentioned preparation method.
In addition, ruthenium nickel combination electrode made from the above method or above-mentioned ruthenium nickel are multiple the present invention also provides a kind of application
Application of the composite electrode in Direct Ammonia Tubular Solid Oxide Fuel Cell.
Technical solution of the present invention has the advantages that
1. the preparation method of ruthenium nickel combination electrode provided by the invention, this method include by the precursor solution drop coating of ruthenium extremely
It on nickel base electrode ontology, is dried after standing, after being then successively fired, cooling down, the Ni-based combination electrode of ru oxide is made, repeats
Above-mentioned steps are until the content of ruthenium is 0.5-3wt% in nickel base electrode ontology, and finally to treated, ru oxide is Ni-based compound
Electrode is restored, and ruthenium nickel combination electrode is made.The ammonolysis craft catalytic activity and electric conductivity of electrode made from this method are preferable, this
It is that more catalysis and electro-chemical activity point can be provided, reaction interface is improved, make electricity because ruthenium is submicron order scale
The ammonolysis craft catalytic activity and electrochemical oxidation reactions rate of pole are promoted, while ruthenium can form of submicron order on the electrode
Granulosa provides new electrical conductance path for SOFC electrode, to improve the electric conductivity of electrode；In addition, the electrode have compared with
Good ammonolysis craft catalytic activity, can provide more hydrogen for battery, and ruthenium-based catalyst has preferable low temperature active, makes battery
Low temperature electrochemical performance be improved.
2. the preparation method of ruthenium nickel combination electrode provided by the invention, the carrier that this method uses both can be used as electrode sheet
The ionic conductor material of body can further enrich the three phase boundary of electrochemical reaction, promote the generation of electrochemical reaction；The load
Body can also be used as the carrier of ruthenium load, and load stability is preferable.
3. the preparation method of ruthenium nickel combination electrode provided by the invention, by limit heating rate in electrode production process,
Maturing temperature, calcining time, reduction temperature and recovery time, can make ruthenium load capacity and dispersion degree promoted, enhance ruthenium and from
The load stability and catalytic activity that sub- conductor carrier is shown in.
4. ruthenium nickel combination electrode provided by the invention, which has preferable ammonia catalytic activity and chemical property.
5. application of the electrode provided by the invention in direct ammonia SOFC, the electrode can be used as the sun of direct ammonia SOFC
Pole promotes the ammonia catalytic activity and entirety chemical property of direct ammonia SOFC.
Specific embodiment
There is provided following embodiments is to preferably further understand the present invention, it is not limited to the best embodiment party
Formula is not construed as limiting the contents of the present invention and protection scope, anyone under the inspiration of the present invention or by the present invention and its
The feature of his prior art is combined and any and identical or similar product of the present invention for obtaining, all falls within of the invention
Within protection scope.
Specific experiment step or condition person are not specified in embodiment, according to the literature in the art described routine experiment
The operation of step or condition can carry out.Reagents or instruments used without specified manufacturer, being can be by commercially available acquisition
Conventional reagent product.
The preparation method of nickel base electrode ontology includes: the first material and the second material according to the uniformly mixed ball milling of its mass ratio
Afterwards, dry-pressing formed at 6~15MPa, then the isostatic cool pressing at 200~300MPa, then under air conditions, at 500~600 DEG C
Nickel base electrode ontology is made after 5~10h of lower pre-burning；In the examples below, the first material and the second material are according to its mass ratio
It is dry-pressing formed at 10MPa after being uniformly mixed ball milling, then the isostatic cool pressing at 200MPa, then under air conditions, at 550 DEG C
Nickel base electrode ontology is made after lower pre-burning 10h.
Embodiment 1
A kind of preparation method of ruthenium nickel combination electrode is present embodiments provided, including,
Nickel base electrode ontology (the quality m that the present embodiment is used1) it include the first material and the second material, the first material is
YSZ, the second material are nickel oxide, and the mass ratio of the first material and the second material is 4:6；The content of ruthenium is in ruthenium nickel combination electrode
1wt%；
Preparation method includes,
(1) the nitric acid ruthenium solution 0.3g of 5wt% is weighed, the presoma after 0.3g dehydrated alcohol slightly shakes up as ruthenium is added
Solution for standby stands 1h, then dries 1h at 100 DEG C then by the precursor solution drop coating of ruthenium to nickel base electrode ontology；
(2) 450 DEG C are warming up to the heating rate of 1.2 DEG C/min to be roasted, are down to room temperature after roasting 20min, obtain
The Ni-based combination electrode of ru oxide, the precursor solution of ruthenium can generate ruthenium-oxide (RuO in roasting process2)；
(3) the Ni-based combination electrode of ru oxide, quality m are weighed2, calculate ruthenium in ru oxide Ni-based combination electrode and contain
Amount, repetition step (1) and (2) are 1wt% up to the content of ruthenium in nickel base electrode ontology, that is, meet formula I:
(4) it is passed through hydrogen, by RuO at 800 DEG C2It is reduced to Ru and Ni respectively with NiO, recovery time 30min is obtained
The ruthenium nickel combination electrode；
The present embodiment additionally provides ruthenium nickel combination electrode made from a kind of above method；
Above-mentioned ruthenium nickel combination electrode can be used as anode applied in direct ammonia SOFC.
Embodiment 2
A kind of preparation method of ruthenium nickel combination electrode is present embodiments provided, including,
Nickel base electrode ontology (the quality m that the present embodiment is used1) it include the first material and the second material, the first material is
BCZY, the second material are nickel oxide, and the mass ratio of the first material and the second material is 7:13；The content of ruthenium in ruthenium nickel combination electrode
For 0.5wt%；
Preparation method includes,
(1) 0.05g ruthenic chloride is weighed, the precursor solution being added after 0.4g deionized water slightly shakes up as ruthenium is spare,
Then by the precursor solution drop coating of ruthenium to nickel base electrode ontology, 1.2h is stood, then dries 0.4h at 120 DEG C；
(2) 500 DEG C are warming up to the heating rate of 1.0 DEG C/min to be roasted, are down to room temperature after roasting 15min, obtain
The Ni-based combination electrode of ru oxide, the precursor solution of ruthenium can generate ruthenium-oxide (RuO in roasting process2)；
(3) the Ni-based combination electrode of ru oxide, quality m are weighed2, calculate ruthenium in ru oxide Ni-based combination electrode and contain
Amount, repetition step (1) and (2) are 0.5wt% up to the content of ruthenium in nickel base electrode ontology, that is, meet formula I:
(4) it is passed through hydrogen, by RuO at 600 DEG C2It is reduced to Ru and Ni respectively with NiO, recovery time 2h obtains institute
State ruthenium nickel combination electrode；
The present embodiment additionally provides ruthenium nickel combination electrode made from a kind of above method；
Above-mentioned ruthenium nickel combination electrode can be used as anode applied in direct ammonia SOFC.
Embodiment 3
A kind of preparation method of ruthenium nickel combination electrode is present embodiments provided, including,
Nickel base electrode ontology (the quality m that the present embodiment is used1) it include the first material and the second material, the first material is
GDC, the second material are nickel oxide, and the mass ratio of the first material and the second material is 9:11；The content of ruthenium in ruthenium nickel combination electrode
For 3wt%；
Preparation method includes,
(1) the nitric acid ruthenium 0.5g that mass fraction is 5wt% is weighed, is added after 0.3g dehydrated alcohol slightly shakes up as ruthenium
Precursor solution is spare, then by the precursor solution drop coating of ruthenium to nickel base electrode ontology, stands 0.5h, then dries at 80 DEG C
Dry 1.2h；
(2) 500 DEG C are warming up to the heating rate of 1.5 DEG C/min to be roasted, are down to room temperature after roasting 20min, obtain
The Ni-based combination electrode of ru oxide, the precursor solution of ruthenium can generate ruthenium-oxide (RuO in roasting process2)；
(3) the Ni-based combination electrode of ru oxide, quality m are weighed2, calculate ruthenium in ru oxide Ni-based combination electrode and contain
Amount, repetition step (1) and (2) are 3wt% up to the content of ruthenium in nickel base electrode ontology, that is, meet formula I:
(4) it is passed through hydrogen, by RuO at 700 DEG C2It is reduced to Ru and Ni respectively with NiO, recovery time 1h obtains institute
State ruthenium nickel combination electrode；
The present embodiment additionally provides ruthenium nickel combination electrode made from a kind of above method；
Above-mentioned ruthenium nickel combination electrode can be used as anode applied in direct ammonia SOFC.
Embodiment 4
A kind of preparation method of ruthenium nickel combination electrode is present embodiments provided, including,
Nickel base electrode ontology (the quality m that the present embodiment is used1) it include the first material and the second material, the first material is
BCZYYb, the second material are nickel oxide, and the mass ratio of the first material and the second material is 6:4；Ruthenium contains in ruthenium nickel combination electrode
Amount is 2wt%；
Preparation method includes,
(1) 0.1g acetic acid ruthenium is weighed, the precursor solution being added after 0.4g dehydrated alcohol slightly shakes up as ruthenium is spare, so
Afterwards by the precursor solution drop coating of ruthenium to nickel base electrode ontology, 1.5h is stood, then dries 0.8h at 90 DEG C；
(2) 480 DEG C are warming up to the heating rate of 1.3 DEG C/min to be roasted, are down to room temperature after roasting 30min, obtain
The Ni-based combination electrode of ru oxide, the precursor solution of ruthenium can generate ruthenium-oxide (RuO in roasting process2)；
(3) the Ni-based combination electrode of ru oxide, quality m are weighed2, calculate ruthenium in ru oxide Ni-based combination electrode and contain
Amount, repetition step (1) and (2) are 2wt% up to the content of ruthenium in nickel base electrode ontology, that is, meet formula I:
(4) it is passed through hydrogen, by RuO at 650 DEG C2It is reduced to Ru and Ni respectively with NiO, recovery time 1.5h is obtained
The ruthenium nickel combination electrode；
The present embodiment additionally provides ruthenium nickel combination electrode made from a kind of above method；
Above-mentioned ruthenium nickel combination electrode can be used as anode applied in direct ammonia SOFC.
Embodiment 5
A kind of preparation method of ruthenium nickel combination electrode is present embodiments provided, including,
Nickel base electrode ontology (the quality m that the present embodiment is used1) it include the first material and the second material, the first material is
BZY, the second material are nickel oxide, and the mass ratio of the first material and the second material is 3:7；In the compound preparing hydrogen by ammonia decomposition electrode of ruthenium nickel
The content of ruthenium is 2.5wt%；
Preparation method includes,
(1) 0.1g acetylacetone,2,4-pentanedione ruthenium is weighed, the precursor solution being added after 0.3g dehydrated alcohol slightly shakes up as ruthenium is standby
With then by the precursor solution drop coating of ruthenium to nickel base electrode ontology, then standing 0.8h dries 1h at 110 DEG C；
(2) 430 DEG C are warming up to the heating rate of 1.2 DEG C/min to be roasted, are down to room temperature after roasting 25min, obtain
The Ni-based combination electrode of ru oxide, the precursor solution of ruthenium can generate ruthenium-oxide (RuO in roasting process2)；
(3) the Ni-based combination electrode of ru oxide, quality m are weighed2, calculate ruthenium in ru oxide Ni-based combination electrode and contain
Amount, repetition step (1) and (2) are 2.5wt% up to the content of ruthenium in nickel base electrode ontology, that is, meet formula I:
(4) it is passed through hydrogen, by RuO at 600 DEG C2It is reduced to Ru and Ni respectively with NiO, recovery time 2h obtains institute
State ruthenium nickel combination electrode；
The present embodiment additionally provides ruthenium nickel combination electrode made from a kind of above method；
Above-mentioned ruthenium nickel combination electrode can be used as anode applied in direct ammonia SOFC.
Test example
This test example provides electrode made from embodiment 1-5 and surveys as the chemical property of direct ammonia SOFC anode electrode
Examination and test result, the specific test method is as follows, and test result is shown in Table 1；Wherein, blank group 1 is the nickel base electrode in embodiment 1
Ontology is the nickel base electrode ontology in embodiment 2 as direct ammonia SOFC anode as direct ammonia SOFC anode electrode, blank group 2
Electrode；
The preparation method of direct ammonia SOFC in this test example includes the following steps,
The preparation of electrolyte slurry and cathode slurry: by yttria-stabilized zirconia, nickel oxide and triethanolamine mixing ball
After mill, electrolyte slurry is obtained；Cathode slurry will be obtained after lanthanum-strontium manganese, terpinol and ethyl cellulose mixing and ball milling；
Direct ammonia SOFC preparation: electrolyte slurry is uniformly coated on anode electrode using the method for spin coating, is obtained
Anode support with electrolyte thin membrane structure then in air, forms electrolytic thin-membrane after roasting 10h at 1200 DEG C,
Then cathode slurry is coated on electrolytic thin-membrane using silk screen print method, forms yin after roasting 4h at 1100 DEG C after drying
Pole electrode；Then it places it under hydrogen atmosphere, is restored at 700 DEG C, obtain direct ammonia SOFC.
The test method of chemical property: direct ammonia SOFC anode is passed through 20mL/min ammonia, and cathode is passed through 50mL/min sky
Gas tests the corresponding current value of SOFC at 600 DEG C, 0.7V, and current value is bigger, and electrochemistry is better；
The test method of ammonolysis craft efficiency: it is dense that the ammonia exported under 20mL/min ammonia flow under open-circuit voltage is tested by chromatography
Degree；
The performance test results of electrode made from 1 embodiment 1-2 of table and comparative example 1
| Example | Chemical property (A) | Ammonolysis craft efficiency (%) |
| Blank group 1 | 0.48 | 21 |
| Blank group 2 | 0.65 | 36 |
| Embodiment 1 | 0.55 | 53 |
| Embodiment 2 | 0.96 | 72 |
| Embodiment 3 | 0.75 | 58 |
| Embodiment 4 | 0.78 | 62 |
| Embodiment 5 | 0.80 | 63 |
In table 1, embodiment 1 illustrates the chemical property and ammonolysis craft of electrode made from the present embodiment compared with blank group 1
Efficiency is preferable；Embodiment 2 illustrates the chemical property and ammonolysis craft efficiency of electrode made from the present embodiment compared with blank group 2
Preferably；The chemical property and ammonolysis craft efficiency of electrode made from embodiment 3- embodiment 5 are preferable.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And thus amplify out it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of preparation method of ruthenium nickel combination electrode, which is characterized in that including,
(1) by the precursor solution drop coating of ruthenium to nickel base electrode ontology, after standing, drying；
(2) nickel base electrode ontology is successively roasted and is cooled down, the Ni-based combination electrode of ru oxide is made；
(3) content of ruthenium in the Ni-based combination electrode of the ru oxide is weighed and calculated, repeats step (1) and (2) until described
The content of ruthenium is 0.5-3wt% in nickel base electrode ontology；
(4) to step (3), treated that the Ni-based combination electrode of ru oxide restores, and ruthenium nickel combination electrode is made.
2. preparation method according to claim 1, which is characterized in that the nickel base electrode ontology includes electrode slice and setting
Electrolyte layer thereon, the electrolyte layer include the first material and the second material, and first material is barium based perovskite, oxygen
Change one of zirconium base rare-earth oxide, cerium oxide base rare-earth oxide, lanthanum gallate based perovskite；Second material
Material is nickel source；
The oxidation zirconium base rare-earth oxide is yttria-stabilized zirconia or scandium oxide-stabilizing zirconia；
The cerium oxide base rare-earth oxide is the cerium oxide of Gd2 O3 or the cerium oxide of strontium doping；
The barium based perovskite is zirconium doped yttrium barium cerate, zirconium yttrium ytterbium doping barium cerate or doped yttrium barium zirconate；
The lanthanum gallate based perovskite is the lanthanum gallate of zirconium, strontium and magnesium doping.
3. preparation method according to claim 2, which is characterized in that the mass ratio of first material and the second material is
3:7-6:4。
4. preparation method according to claim 1-3, which is characterized in that before in the precursor solution of the ruthenium
Drive body is at least one of ruthenic chloride, nitric acid ruthenium, acetic acid ruthenium or acetylacetone,2,4-pentanedione ruthenium；
The solvent of the precursor solution of the ruthenium is water or ethyl alcohol；The mass fraction of presoma is in the precursor solution of the ruthenium
3-15%.
5. preparation method according to claim 1-4, which is characterized in that the time of the standing is 0.5-
1.5h；
The drying temperature is 80-120 DEG C, drying time 0.4-1.2h.
6. preparation method according to claim 1-5, which is characterized in that the temperature of the roasting is 400-500
DEG C, the time of the roasting is 15-30min.
7. preparation method according to claim 1-6, which is characterized in that before the roasting, further include with
The step of nickel base electrode ontology is warming up to 400-500 DEG C by the heating rate of 1-1.5 DEG C/min.
8. preparation method according to claim 1-7, which is characterized in that the reduction is to handle step (3)
Ru oxide afterwards Ni-based combination electrode is placed in carry out under atmosphere of hydrogen；
The temperature of the reduction is 600-800 DEG C, time 0.5-2h.
9. a kind of ruthenium nickel combination electrode, which is characterized in that be made using the described in any item preparation methods of claim 1-8.
10. a kind of application, which is characterized in that ruthenium nickel combination electrode or right made from any one of claim 1-8 the method
It is required that application of the ruthenium nickel combination electrode in Direct Ammonia Tubular Solid Oxide Fuel Cell described in 9.
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| CN116474792A (en) * | 2023-04-20 | 2023-07-25 | 南京工业大学 | Catalytic material for producing hydrogen from ammonia, preparation method and application |
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