CN104752734B - Low-temperature solid oxide fuel cell cathode in core-shell nano fiber structure and electrostatic spinning preparation method thereof - Google Patents
Low-temperature solid oxide fuel cell cathode in core-shell nano fiber structure and electrostatic spinning preparation method thereof Download PDFInfo
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- 239000011258 core-shell material Substances 0.000 title claims abstract description 36
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000010041 electrostatic spinning Methods 0.000 title claims abstract description 19
- 239000000446 fuel Substances 0.000 title claims abstract description 12
- 239000007787 solid Substances 0.000 title abstract description 3
- 238000009987 spinning Methods 0.000 claims abstract description 70
- 239000002243 precursor Substances 0.000 claims abstract description 43
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- 239000001301 oxygen Substances 0.000 claims abstract description 42
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 42
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- 238000002156 mixing Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 12
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 11
- 238000013019 agitation Methods 0.000 claims description 11
- 229910021645 metal ion Inorganic materials 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 10
- 239000012046 mixed solvent Substances 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 9
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- 238000002242 deionisation method Methods 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
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- 239000004567 concrete Substances 0.000 claims description 2
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- 239000003795 chemical substances by application Substances 0.000 claims 2
- 230000005611 electricity Effects 0.000 claims 1
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- 229920006316 polyvinylpyrrolidine Polymers 0.000 claims 1
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- 239000002078 nanoshell Substances 0.000 abstract 1
- 230000001988 toxicity Effects 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- 229910002607 Gd0.1Ce0.9O1.95 Inorganic materials 0.000 description 15
- 239000010410 layer Substances 0.000 description 15
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- 239000000463 material Substances 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
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- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
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- 229910002741 Ba0.5Sr0.5Co0.8Fe0.2O3-δ Inorganic materials 0.000 description 1
- 229910002742 Ba0.5Sr0.5Co0.8Fe0.2O3−δ Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002187 La0.8Sr0.2CoO3 Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 230000002708 enhancing effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 206010023497 kuru Diseases 0.000 description 1
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- 230000010287 polarization Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
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- 238000005382 thermal cycling Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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Classifications
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
-
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Electrochemistry (AREA)
- Composite Materials (AREA)
- Physics & Mathematics (AREA)
- Textile Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
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- Inert Electrodes (AREA)
- Multicomponent Fibers (AREA)
Abstract
The invention relates to a low-temperature solid oxide fuel cell cathode in a core-shell nano fiber structure and an electrostatic spinning preparation method and belongs to the field of functional materials. The core-shell nano fiber structure cathode consists of a nano fiber core and a nano shell layer, wherein the fiber core and the shell layer respectively consist of a perovskite structure ion-electron mixed conductor component A and an oxygen ion conductor electrolyte component B or consist of opposite components; the core-shell nano fiber cathode is prepared in an electrostatic spinning manner, a component A before-spinning precursor solution and a component B before-spinning precursor solution are respectively prepared and then are respectively injected into an inner-layer spinning passage or an outer-layer spinning passage so as to carry out the spinning, and composite fibers are dried and sintered at a high temperature to obtain the core-shell nano fiber structure cathode material. By adopting the core-shell nano fiber structure, the oxygen reduction catalytic activity, anti-CO2 surface adsorption toxicity capacity and structural and performance stability of the low-temperature SOFC cathode are improved; moreover, the process is simple, and the cost is low.
Description
Technical field
The present invention relates to low temperature solid-state oxide fuel battery cathode and its Static Spinning in a kind of core-shell structure copolymer nanofibrous structures
Silk preparation method, belongs to field of functional materials.
Background technology
SOFC (sofc) is a kind of green alternative energy source of great application prospect, by operating temperature by
1000 DEG C of high temperature are reduced to low temperature range in 500-700 DEG C, are the important development directions in current sofc field.With sofc work
The reduction of temperature, the oxygen reduction catalytic activity of negative electrode declines, and polarization impedance increases rapidly, becomes low temperature sofc output work in restriction
The key factor of rate；The reduction of operating temperature is also by the co of aggravation cathode surface2Absorption poisons, and leads to cathode catalytic activity to enter one
Step declines, and sofc internal loss increases；Additionally, the matched coefficients of thermal expansion between negative electrode and electrolyte also affects sofc system
Standby with Thermal Cycling in structure and stability.Therefore, research and development have high hydrogen reduction in 500-700 DEG C of temperature range and urge
Change active, anti-co2During the cathode material that surface adsorption poisons and thermal coefficient of expansion is matched with electrolyte is for promoting
The development of low temperature sofc is significant with application.
Chen et al. (yan chen, zhuhua cai, yener kuru, wen ma, harry l.tuller,
Bilge yildiz, advanced energy materials, 2013,3,1221.) utilize pumping laser deposition technique
It is prepared for la0.8sr0.2coo3/ (la0.5sr0.5)2coo4Heterogeneous interface structure plural layers, oxygen reduction reaction speed at 500 DEG C
Improve several magnitudes, the oxygen reduction catalytic activity of negative electrode significantly increases, but this multilayered film material needs expensive, special system
Standby equipment, high cost, it is unfavorable for batch production and the large-scale application of negative electrode, and the co of negative electrode can not be solved2Surface adsorption
Poison the high problem with thermal coefficient of expansion.Zhou et al. (wei zhou, fengli liang, zongping shao,
Zhonghua zhu, scientific reports, 2012,2: 327) added using solution infiltration-microwave plasma
Thermal means is in ba0.5sr0.5co0.8fe0.2o3-δ(bscf) particle surface preparation la2nio4+δProtective layer, improves bscf negative electrode and exists
Containing co2Oxygen reduction reaction catalysis activity in atmosphere and stability, for solving alkaline including earth metal ion perovskite negative electrode
co2Surface adsorption poisoning problem provides effective solution, but, due to la2nio4+δThe oxygen ionic conductivity of protective layer
Low, it is unfavorable for the oxygen surface exchange process of negative electrode, lead to the oxygen reduction catalytic activity of prepared negative electrode not high, and still exist
The too high problem of thermal coefficient of expansion.
Content of the invention
In order to overcome problems of the prior art, the present invention provides low-temperature solid in a kind of core-shell structure copolymer nanofibrous structures
State oxide fuel battery cathode and its electrostatic spinning preparation method, by constructing low temperature in the enhancing of core-shell structure copolymer nanofibrous structures
The oxygen reduction catalytic activity of solid-oxide fuel cell negative electrode, anti-co2It is steady with performance that surface adsorption poisons ability and structure
Qualitative, and be prepared using electrostatic spinning, simplify preparation technology, reduce preparation cost.
The technical solution used in the present invention is: low temperature solid-state oxide fuel cell in a kind of core-shell structure copolymer nanofibrous structures
Negative electrode, described core-shell structure copolymer nanofibrous structures negative electrode is made up of with nanometer outer shell nanofiber core, described nanofiber core with receive
Rice outer shell is respectively by perovskite structure ion-electron mixing conductor oxide component a and oxygen ion conductor electrolyte components b structure
Become, or on the contrary, a nanometer outer shell, oxygen ion conductor are constituted by perovskite structure ion-electron mixing conductor oxide component a
Electrolyte components b constitutes nanofiber core；In described nanofibrous structures, nanofiber nuclear diameter is 50-500 nanometer, nanometer
Outer shell thickness is 100-800 nanometer.
The electrostatic spinning preparation method of low temperature solid-state oxide fuel battery cathode in a kind of core-shell structure copolymer nanofibrous structures,
Prepare perovskite structure ion-electron mixing conductor oxide component a spinning precursor solution and oxygen ion conductor first respectively
Then two kinds of spinning precursor solutions are injected separately into internal layer and outer layer slinning cabinet by electrolyte components b spinning precursor solution
Interior, or perovskite structure ion-electron mixing conductor oxide component a spinning precursor solution and oxygen ion conductor are electrolysed
Matter component b spinning precursor solution injects contrary slinning cabinet, carries out coaxial spinning, prepares concentric composite fibre, and fiber is through dry
Dry, high temperature sintering, obtains by perovskite structure ion-electron mixing conductor oxide component a and oxygen ion conductor electrolyte group
Divide two kinds that b is constituted different core-shell structure copolymer nanofibrous structures cathode materials；Core-shell structure copolymer nanofibrous structures negative electrode of the present invention
Concrete preparation process as follows:
Step one, respectively preparation perovskite structure ion-electron mixing conductor oxide component a spinning precursor solution
With oxygen ion conductor electrolyte components b spinning precursor solution；
Perovskite structure ion-electron mixing conductor oxide component a spinning precursor solution process for preparation:
According to the stoichiometric proportion of perovskite structure oxide, weigh the required acetate containing respective metal ion or nitre
Silicate reagent, is dissolved in deionization ethanol-water-n, in n- dimethylformamide mixed solvent, then stirs in magnetic force under magnetic agitation
Mix and lower Polyvinylpyrrolidone is dissolved in solution mixed above；Or, under magnetic stirring that Polyvinylpyrrolidone is molten first
In deionization ethanol-water-n, n- dimethylformamide mixed solvent, then again by the required acetic acid containing respective metal ion
Salt or nitrate reagent add, magnetic agitation is to being completely dissolved；Deionized water, ethanol and n in mixed solution, n- dimethyl formyl
The volume ratio of amine solvent is 0.1-0.5:0.5-1: 5-10, and the consumption of Polyvinylpyrrolidone is vinegar in solution mixed above
1.5-3 times of hydrochlorate and nitrate reagent gross mass；The perovskite structure oxide spinning precursor solution of mix homogeneously is surpassed
Sound removes bubble, places 5-15 hour at room temperature；
Oxygen ion conductor electrolyte components b spinning precursor solution process for preparation:
According to the stoichiometric proportion of electrolyte oxide, weigh the required acetate containing respective metal ion or nitrate
Reagent, it is dissolved in deionization ethanol-water-n under magnetic agitation, in n- dimethylformamide mixed solvent, then by polyvinyl pyrrole
Alkanone is dissolved in solution mixed above；Or, first Polyvinylpyrrolidone is dissolved in deionization ethanol-water-n, n- dimethyl methyl
In amide mixed solvent, then again by the required acetate containing respective metal ion or the addition of nitrate reagent, magnetic agitation
To being completely dissolved；Deionized water, ethanol and n in mixed solution, the volume ratio of n- solvent dimethylformamide is 0.1-0.5:
0.5-1: 5-10, the consumption of Polyvinylpyrrolidone is acetate and nitrate reagent gross mass in solution mixed above
1.5-3 again；Obtain oxygen ion conductor electrolyte spinning precursor solution, remove bubble by ultrasonic for solution 2, place 5-15 at room temperature
Hour；
Step 2, the electrostatic spinning preparation of core-shell structure copolymer nanofiber
Respectively will be molten for the perovskite structure preparing above ion-electron mixing conductor oxide component a spinning presoma
Liquid and oxygen ion conductor electrolyte components b spinning precursor solution inject in internal layer and the outer layer channel of electrostatic spinning head, carry out
Coaxial injection, spinning condition: the flow velocity 5-30 μ l/min of spinning liquid, spinning voltage 10-25kv, spinning syringe needle and accepter
Spacing 5-15cm；Before the core-shell configuration of nanofiber is by perovskite structure ion-electron mixing conductor oxide component a spinning
Drive liquid solution and oxygen ion conductor electrolyte components b spinning precursor solution to determine in the injection phase of internal layer and outer layer channel,
The thickness of diameter fibronuclear in nanofiber and outer shell is carried out with the flow velocity of two kinds of spinning liquid by changing spinning voltage
Regulation and control, obtain the concentric composite fibre of heteroid core-shell structure copolymer, then by fiber in 40-80 DEG C of drying baker dried 10-20
Hour；
Step 3, core-shell structure copolymer nanofiber negative electrode sinter phase into
After being dried above, composite fibre carries out high temperature sintering with one heart, and sintering condition is: with 3-6 DEG C/min of heating rate
It is heated to 400-600 DEG C, is incubated 2-5 hour, be then heated to 1000-1150 DEG C with 5-10 DEG C/min of speed and to be incubated 1-5 little
When, finally room temperature is cooled to 5-12 DEG C/min of speed, in this high-temperature sintering process, perovskite structure oxide component with
Oxygen ion conductor electrolyte components each become phase, form core-shell structure copolymer nanofiber cathode material.
For ease of being further described above-mentioned technical scheme, perovskite structure ion-electron mixing conductor oxide component a
Referred to as component a, oxygen ion conductor electrolyte components b is referred to as component b.
The invention has the beneficial effects as follows:
1. in the core-shell structure copolymer nanofibrous structures described in low temperature solid-state oxide fuel battery cathode by nanofiber core with receive
Rice outer shell is constituted, and fiber core is respectively component a and component b with outer shell, or component is contrary；Component a is cathodic oxygen reduction
Reaction provides required electronics, oxonium ion, and component b is oxygen ion conductor material, the addition of component b can improve the oxygen of negative electrode from
Electron conductivity, oxygen surface exchange and transfer rate, strengthen the oxygen reduction catalytic activity of negative electrode；Component b can also reduce negative electrode
Thermal coefficient of expansion, also will improve the anti-co of negative electrode as protective layer2Surface adsorption poisons ability, thus improve the structure of sofc with
Stability；And nanofiber is configured to increase electrode reaction active area, promotes oxygen surface exchange and bulk diffusion speed,
Further enhance the oxygen reduction catalytic activity of negative electrode, in optimization, low temperature solid-state oxide fuel battery cathode material is comprehensive
Energy.
2. two kinds of different component spinning precursor solutions are carried out electrostatic spinning by an offer method, synchronization sinters phase into, obtain
Obtain low temperature solid-state oxide fuel battery cathode in the nanofibrous structures being made up of nanofiber core, nanometer with nanometer outer shell
Fiber core and nanometer outer shell construct by injection phase decision, fibronuclear diameter and the outer shell of two kinds of spinning precursor solutions
Thickness by change spinning voltage easily regulated and controled with the flow velocity of two kinds of spinning liquid, preparation process is simple, cost is relatively low.
Brief description
Fig. 1 is a kind of electrostatic spinning schematic diagram.Component a spinning precursor solution is with component b spinning precursor solution respectively
Injection internal layer and outer layer channel.
Fig. 2 isAs shown in Figure 1The core-shell structure copolymer nanofiber side of electrospinning device preparation and cross section structure schematic diagram.Group
Divide a as fiber core, component b is as outer shell.
Fig. 3 is another kind of electrostatic spinning schematic diagram.Component a spinning precursor solution is divided with component b spinning precursor solution
Zhu Ru not outer layer and inner-layer channel.
Fig. 4 isAs shown in Figure 3The core-shell structure copolymer nanofiber side of electrospinning device preparation and cross section structure schematic diagram.Group
Divide a as outer shell, component b is as fiber core.
Specific embodiment
It is described further below by specific embodiment.
Prepared by perovskite oxide prba using electrospinning process0.92co2o6-δ(δ is oxygen deficit) and electrolyte
gd0.1ce0.9o1.95Low temperature sofc cathode material in the core-shell structure copolymer nanofibrous structures constituting
Step one, respectively preparation prba0.92co2o6-δSpinning precursor solution and gd0.1ce0.9o1.95Spinning precursor solution
prba0.92co2o6-δSpinning precursor solution process for preparation:
According to synthesis 0.4mmol prba0.92co2o6-δMetal ion metering than accurately weighing pr (no3)3▪6h2o
0.174g、ba(no3)20.0961g、co(ac)2▪4h2O 0.199g, puts into by 0.2ml deionized water, 0.5ml ethanol and 6ml
N, n- dimethylformamide constitute mixed solvent in, at room temperature magnetic agitation to above reagent be completely dissolved, mix homogeneously；
Then 1.0 grams of Polyvinylpyrrolidone are dissolved in solution mixed above under magnetic stirring, are uniformly mixed
prba0.92co2o6-δSpinning precursor solution, removes bubble by ultrasonic for solution, places 10 hours at room temperature；
Electrolyte gd0.1ce0.9o1.95Spinning precursor solution process for preparation:
0.35 gram of Polyvinylpyrrolidone is dissolved in by 0.2ml deionized water, 0.5ml ethanol and 2ml n, n- dimethyl methyl
In the mixed solvent that amide is constituted, magnetic agitation is to being completely dissolved at room temperature；According to synthesis 0.4mmol gd0.1ce0.9o1.95
Metal ion metering ratio weigh 0.156 gram of ce (no3)3▪6h2O, 0.018 gram of gd (no3)3▪6h2O, adds solution mixed above
In, under room temperature, magnetic agitation, to being completely dissolved, obtains electrolyte gd0.1ce0.9o1.95Spinning precursor solution, will be ultrasonic for solution 2
Remove bubble, place 10 hours at room temperature.
Step 2, prba0.92co2o6-δ-gd0.1ce0.9o1.95The electrostatic spinning preparation of core-shell structure copolymer nanofiber
Respectively by the prba preparing above0.92co2o6-δSpinning precursor solution and gd0.1ce0.9o1.95Spinning presoma
Solution injects in internal layer and the outer layer channel of electrostatic spinning syringe, and the spacing adjusting spinning syringe needle with accepter is 10cm, plus
High pressure 10-15 kv is coaxially sprayed, and controls prba using syringe pump0.92co2o6-δSolution and gd0.1ce0.9o1.95The stream of solution
Speed is 5-20 μ l/min, and coaxial spinning obtains prba0.92co2o6-δGroup is divided into fiber core, gd0.1ce0.9o1.9Group is divided into outer shell
Nanofiber；Change the injection phase of two kinds of spinning precursor solutions, will gd0.1ce0.9o1.95Solution injects electrostatic spinning
The inner-layer channel of syringe, and prba0.92co2o6-δSolution injects outer layer channel, carries out electrostatic spinning, then obtains
gd0.1ce0.9o1.9Group is divided into fiber core, prba0.92co2o6-δGroup is divided into the concentric composite fibre of outer shell；By obtain
prba0.92co2o6-δ-gd0.1ce0.9o1.95Composite fibre dried 20 hours in 60 DEG C of drying baker with one heart.
Step 3, prba0.92co2o6-δ-gd0.1ce0.9o1.95Composite fibre negative electrode sinters phase into one heart
Prba after being dried above0.92co2o6-δ-gd0.1ce0.9o1.95Composite fibre carries out high temperature sintering, first with 3 with one heart
DEG C/min heating rate is heated to 600 DEG C, is incubated 3 hours, is then heated to 1050 DEG C with 5 DEG C/min of speed and to be incubated 2 little
When, finally it is cooled to room temperature with 10 DEG C/min of speed, obtain two kinds of heteroid prba0.92co2o6-δ-gd0.1ce0.9o1.95
Core-shell structure copolymer nanofiber cathode material, wherein prba0.92co2o6-δFor orthorhombic phase laminated perovskite structure, gd0.1ce0.9o1.95For face
The heart cube phase structure.The prba obtaining0.92co2o6-δ-gd0.1ce0.9o1.95Core-shell structure copolymer nanofiber negative electrode is in 500-700 DEG C of temperature
Lower oxygen reduction catalytic activity strengthens 30-80%, and thermal coefficient of expansion reduces 20-40%, anti-co2Surface adsorption poisons ability and improves 40-
70%, negative electrode combination property improves.
Claims (1)
1. in a kind of core-shell structure copolymer nanofibrous structures low temperature solid-state oxide fuel battery cathode electrostatic spinning preparation method, institute
The core-shell structure copolymer nanofibrous structures negative electrode stated is made up of with nanometer outer shell nanofiber core, outside described nanofiber core and nanometer
Shell is made up of perovskite structure ion-electron mixing conductor oxide component a and oxygen ion conductor electrolyte components b respectively,
Or contrary, it is made up of a nanometer outer shell, oxygen ion conductor electricity perovskite structure ion-electron mixing conductor oxide component a
Solution matter component b constitutes nanofiber core；In described nanofibrous structures, nanofiber nuclear diameter is 50-500 nanometer, outside nanometer
Shell thickness is 100-800 nanometer；It is characterized in that, described preparation method: prepare perovskite structure ion-electron first respectively
Mixed-conducting oxides component a spinning precursor solution and oxygen ion conductor electrolyte components b spinning precursor solution, then will
Two kinds of spinning precursor solutions are injected separately in internal layer and outer layer slinning cabinet, or perovskite structure ion-electron is mixed
Conducting oxide component a spinning precursor solution and the contrary spinning of oxygen ion conductor electrolyte components b spinning precursor solution injection
Silk passage, carries out coaxial spinning, prepare concentric composite fibre, fiber drying, high temperature sintering, acquisition by perovskite structure from
Two kinds of different core-shell structure copolymer nanofibers that son-electron mixed conductor oxide component a is constituted with oxygen ion conductor electrolyte components b
Structure cathode material；The concrete preparation process of core-shell structure copolymer nanofibrous structures negative electrode of the present invention is as follows:
Step one, respectively preparation perovskite structure ion-electron mixing conductor oxide component a spinning precursor solution and oxygen
Ion conductor electrolyte components b spinning precursor solution；
Perovskite structure ion-electron mixing conductor oxide component a spinning precursor solution process for preparation:
According to the stoichiometric proportion of perovskite structure oxide, weigh the required acetate containing respective metal ion or nitrate
Reagent, is dissolved in deionization ethanol-water-n, in n- dimethylformamide mixed solvent, then under magnetic stirring under magnetic agitation
Polyvinylpyrrolidone is dissolved in solution mixed above；Or, under magnetic stirring Polyvinylpyrrolidone is dissolved in first
In ion ethanol-water-n, n- dimethylformamide mixed solvent, then again by the required acetate containing respective metal ion or
Nitrate reagent adds, magnetic agitation is to being completely dissolved；Deionized water, ethanol and n in mixed solution, n- dimethylformamide is molten
The volume ratio of agent is 0.1-0.5:0.5-1: 5-10, and the consumption of Polyvinylpyrrolidone is acetate in solution mixed above
With nitrate reagent gross mass 1.5-3 times；Go ultrasonic for the perovskite structure oxide spinning precursor solution of mix homogeneously
Bubble, places 5-15 hour at room temperature；
Oxygen ion conductor electrolyte components b spinning precursor solution process for preparation:
According to the stoichiometric proportion of electrolyte oxide, weigh the required acetate containing respective metal ion or nitrate examination
Agent, is dissolved in deionization ethanol-water-n, in n- dimethylformamide mixed solvent, then by polyvinylpyrrolidine under magnetic agitation
Ketone is dissolved in solution mixed above；Or, first Polyvinylpyrrolidone is dissolved in deionization ethanol-water-n, n- dimethyl formyl
In amine mixed solvent, then the more required acetate containing respective metal ion or nitrate reagent are added, magnetic agitation extremely
It is completely dissolved；Deionized water, ethanol and n in mixed solution, the volume ratio of n- solvent dimethylformamide is 0.1-0.5:0.5-
1: 5-10, the consumption of Polyvinylpyrrolidone is the 1.5-3 of acetate and nitrate reagent gross mass in solution mixed above
Times；Obtain oxygen ion conductor electrolyte spinning precursor solution, remove bubble by ultrasonic for solution 2, place 5-15 hour at room temperature；
Step 2, the electrostatic spinning preparation of core-shell structure copolymer nanofiber
Respectively by the perovskite structure preparing above ion-electron mixing conductor oxide component a spinning precursor solution and
Oxygen ion conductor electrolyte components b spinning precursor solution injects in internal layer and the outer layer channel of electrostatic spinning head, carries out coaxial
Injection, spinning condition: the spacing of the flow velocity 5-30 μ l/min of spinning liquid, spinning voltage 10-25kv, spinning syringe needle and accepter
5-15cm；The core-shell configuration of nanofiber is by perovskite structure ion-electron mixing conductor oxide component a spinning presoma
Solution and oxygen ion conductor electrolyte components b spinning precursor solution determine in the injection phase of internal layer and outer layer channel, pass through
Change spinning voltage with the flow velocity of two kinds of spinning liquid, the thickness of diameter fibronuclear in nanofiber and outer shell to be regulated and controled,
Obtain the concentric composite fibre of heteroid core-shell structure copolymer, then by fiber in 40-80 DEG C of drying baker dried 10-20 hour；
Step 3, core-shell structure copolymer nanofiber negative electrode sinter phase into
After being dried above, composite fibre carries out high temperature sintering with one heart, and sintering condition is: is heated with 3-6 DEG C/min of heating rate
To 400-600 DEG C, it is incubated 2-5 hour, is then heated to 1000-1150 DEG C with 5-10 DEG C/min of speed and is incubated 1-5 hour,
Finally room temperature is cooled to 5-12 DEG C/min of speed, in this high-temperature sintering process, perovskite structure oxide component and oxygen from
Sub- conductor electrolyte components each become phase, form core-shell structure copolymer nanofiber cathode material.
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| CN105624806B (en) * | 2016-03-31 | 2017-09-19 | 苏州大学 | A kind of bubble electrostatic spinning system for preparing complex fiber material |
| CN105926055B (en) * | 2016-06-23 | 2018-06-15 | 浙江大学 | The electrospinning process of regulation and control micro/nano-fibre configuration of surface in situ |
| CN106142843B (en) * | 2016-07-06 | 2017-08-22 | 大连理工大学 | A kind of coaxial electrical fluid dynamic printing head device |
| CN109930241A (en) * | 2017-12-18 | 2019-06-25 | 中国科学院大连化学物理研究所 | A kind of electrode material and its preparation and application with core-shell structure |
| JP2022530648A (en) | 2019-04-30 | 2022-06-30 | シックスケー インコーポレイテッド | Mechanically alloyed powder raw material |
| CA3153254A1 (en) | 2019-11-18 | 2021-06-17 | 6K Inc. | Unique feedstocks for spherical powders and methods of manufacturing |
| EP4075551A1 (en) * | 2019-12-10 | 2022-10-19 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Electrode material having fiber structure, and preparation and application thereof |
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| CN111370708B (en) * | 2020-03-20 | 2021-09-07 | 四川轻化工大学 | Solid oxide fuel cell electrode and preparation method thereof |
| KR20230029836A (en) | 2020-06-25 | 2023-03-03 | 6케이 인크. | Microcomposite alloy structure |
| WO2022067303A1 (en) | 2020-09-24 | 2022-03-31 | 6K Inc. | Systems, devices, and methods for starting plasma |
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| CN103117404B (en) * | 2013-01-30 | 2015-02-11 | 哈尔滨工业大学 | preparation method of composite anode by one-dimensional nano fibrous lanthanum strontium titanate (LST) anode material |
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