CN104752734A - 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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- CN104752734A CN104752734A CN201510086996.7A CN201510086996A CN104752734A CN 104752734 A CN104752734 A CN 104752734A CN 201510086996 A CN201510086996 A CN 201510086996A CN 104752734 A CN104752734 A CN 104752734A
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- H—ELECTRICITY
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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 electrostatic spinning preparation method thereof in a kind of core-shell structure copolymer nanofibrous structures, belong to field of functional materials.
Background technology
Solid Oxide Fuel Cell (SOFC) is a kind of green alternative energy source having application prospect, and working temperature is reduced to low temperature range in 500-700 DEG C by 1000 DEG C of high temperature, is the important development direction in current SOFC field.Along with the reduction of SOFC working temperature, the oxygen reduction catalytic activity of negative electrode declines, and polarization impedance increases rapidly, becomes the key factor of low temperature SOFC power output in restriction; The reduction of working temperature is also by the CO of aggravation cathode surface
2absorption poisons, and causes cathode catalytic activity to decline further, and SOFC internal loss increases; In addition, the matched coefficients of thermal expansion between negative electrode and electrolyte also affects SOFC preparation and the Structure and Properties stability in Thermal Cycling.Therefore, research and develop, 500-700 DEG C of temperature range, there is high oxygen reduction catalytic activity, anti-CO
2adsorption poisons and the cathode material that matches of thermal coefficient of expansion and electrolyte is significant for the development and apply of low temperature SOFC in promoting.
The people such as Chen (Yan Chen, Zhuhua Cai, Yener Kuru, Wen Ma, Harry L.Tuller, Bilge Yildiz, Advanced Energy Materials, 2013,3,1221.) pumping laser deposition technique is utilized to prepare La
0.8sr
0.2coO
3/ (La
0.5sr
0.5)
2coO
4heterogeneous interface structure plural layers, at 500 DEG C, oxygen reduction reaction speed improves several magnitude, the oxygen reduction catalytic activity of negative electrode significantly strengthens, but this multilayered film material needs costliness, special Preparation equipment, cost is high, be unfavorable for batch production and the large-scale application of negative electrode, and the CO of negative electrode can not be solved
2adsorption poisons and thermal coefficient of expansion high problem.The people such as Zhou (Wei Zhou, Fengli Liang, Zongping Shao, Zhonghua Zhu, Scientific Reports, 2012,2: 327) utilize solution infiltration-microwave plasma heating means at Ba
0.5sr
0.5co
0.8fe
0.2o
3-δ(BSCF) particle surface prepares La
2niO
4+ δprotective layer, improves BSCF negative electrode and is containing CO
2oxygen reduction reaction catalytic activity in atmosphere and stability, for solving the CO of alkaline including earth metal ionized calcium titanium ore negative electrode
2adsorption poisoning problem provides effective solution, but, due to La
2niO
4+ δthe oxygen ionic conductivity of protective layer is low, is unfavorable for the oxygen surface exchange process of negative electrode, causes the oxygen reduction catalytic activity of prepared negative electrode not high, and still there is the too high problem of thermal coefficient of expansion.
Summary of the invention
In order to overcome problems of the prior art, the invention provides low temperature solid-state oxide fuel battery cathode and electrostatic spinning preparation method thereof in a kind of core-shell structure copolymer nanofibrous structures, by constructing oxygen reduction catalytic activity, the anti-CO of low temperature solid-state oxide fuel battery cathode in the enhancing of core-shell structure copolymer nanofibrous structures
2adsorption poisons ability and Structure and Properties stability, and utilizes electrostatic spinning to be prepared, and simplifies preparation technology, reduces preparation cost.
The technical solution used in the present invention is: low temperature solid-state oxide fuel battery cathode in a kind of core-shell structure copolymer nanofibrous structures, described core-shell structure copolymer nanofibrous structures negative electrode is made up of nanofiber core and nanometer outer shell, described nanofiber core and nanometer outer shell are made up of perovskite structure ion-electron mixing conductor oxide component A and oxygen ion conductor electrolyte components B respectively, or it is contrary, form nanometer outer shell by perovskite structure ion-electron mixing conductor oxide component A, oxygen ion conductor electrolyte components B forms nanofiber core; In described nanofibrous structures, nanofiber nuclear diameter is 50-500 nanometer, and 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, first respectively perovskite structure ion-electron mixing conductor oxide component A spinning precursor solution and oxygen ion conductor electrolyte components B spinning precursor solution is prepared, then two kinds of spinning precursor solutions are injected in internal layer and outer slinning cabinet respectively, or perovskite structure ion-electron mixing conductor oxide component A spinning precursor solution and oxygen ion conductor electrolyte components B spinning precursor solution are injected contrary slinning cabinet, carry out coaxial spinning, prepare concentric composite fibre, fiber drying, high temperature sintering, obtain the two kinds of different core-shell structure copolymer nanofibrous structures cathode materials be made up of perovskite structure ion-electron mixing conductor oxide component A and oxygen ion conductor electrolyte components B, 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, take the required acetate containing respective metal ion or nitrate reagent, deionization ethanol-water-N is dissolved under magnetic agitation, in dinethylformamide mixed solvent, then under magnetic stirring polyvinylpyrrolidone is dissolved in above mixed solution; Or, polyvinylpyrrolidone is dissolved in deionization ethanol-water-DMF mixed solvent first under magnetic stirring, and then by the required acetate containing respective metal ion or nitrate reagent adds, magnetic agitation is to dissolving completely; In mixed solution, the volume ratio of deionized water, alcohol and DMF solvent is 0.1-0.5:0.5-1: 5-10, and the consumption of polyvinylpyrrolidone is 1.5-3 times of acetate and nitrate reagent gross mass in above mixed solution; By the ultrasonic bubble that degass of perovskite structure oxide spinning precursor solution mixed, at room temperature place 5-15 hour;
Oxygen ion conductor electrolyte components B spinning precursor solution process for preparation:
According to the stoichiometric proportion of electrolyte oxide, take the required acetate containing respective metal ion or nitrate reagent, be dissolved in deionization ethanol-water-N under magnetic agitation, in dinethylformamide mixed solvent, then polyvinylpyrrolidone is dissolved in above mixed solution; Or, first polyvinylpyrrolidone is dissolved in deionization ethanol-water-DMF mixed solvent, and then by the required acetate containing respective metal ion or nitrate reagent adds, magnetic agitation is to dissolving completely; In mixed solution, the volume ratio of deionized water, alcohol and DMF solvent is 0.1-0.5:0.5-1: 5-10, and the consumption of polyvinylpyrrolidone is 1.5-3 times of acetate and nitrate reagent gross mass in above mixed solution; Obtain oxygen ion conductor electrolyte spinning precursor solution, by ultrasonic for solution 2 bubble that degass, at room temperature place 5-15 hour;
The electrostatic spinning preparation of step 2, core-shell structure copolymer nanofiber
In the internal layer respectively the perovskite structure ion-electron mixing conductor oxide component A spinning precursor solution for preparing above and oxygen ion conductor electrolyte components B spinning precursor solution being injected electrostatic spinning head and outer layer channel, carry out coaxial injection, spinning condition: the flow velocity 5-30 μ l/min of spinning solution, spinning voltage 10-25kV, the spacing 5-15cm of spinning syringe needle and recipient; The core-shell structure copolymer structure of nanofiber is determined in the injection phase of internal layer and outer layer channel by perovskite structure ion-electron mixing conductor oxide component A spinning precursor solution and oxygen ion conductor electrolyte components B spinning precursor solution, regulated and controled by the thickness of flow velocity to diameter fibronuclear in nanofiber and outer shell changing spinning voltage and two kinds of spinning solutions, obtain the concentric composite fibre of heteroid core-shell structure copolymer, then by fiber at 40-80 DEG C of drying box inner drying process 10-20 hour;
Step 3, core-shell structure copolymer nanofiber negative electrode sinter phase into
Above dry rear composite fibre is with one heart carried out high temperature sintering, sintering condition is: be heated to 400-600 DEG C with 3-6 DEG C/min of heating rate, insulation 2-5 hour, then be heated to 1000-1150 DEG C with 5-10 DEG C/min of speed and be incubated 1-5 hour, finally be cooled to room temperature with 5-12 DEG C/min of speed, in this high-temperature sintering process, perovskite structure oxide component respectively has phase of one's own with oxygen ion conductor electrolyte components, forms core-shell structure copolymer nanofiber cathode material.
For ease of introducing above-mentioned technical scheme further, perovskite structure ion-electron mixing conductor oxide component A is referred to as component A, and oxygen ion conductor electrolyte components B is referred to as B component.
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 is made up of nanofiber core and nanometer outer shell, and fiber core and outer shell are respectively component A and B component, or component is contrary; Component A provides required electronics, oxonium ion for Cathodic oxygen reduction, and B component is oxygen ion conductor material, B component add oxygen ionic conductivity, oxygen surface exchange and the transmission rate that can improve negative electrode, strengthen the oxygen reduction catalytic activity of negative electrode; B component can also reduce the thermal coefficient of expansion of negative electrode, also will improve the anti-CO of negative electrode as protective layer
2adsorption poisons ability, thus improves the Structure and Properties stability of SOFC; And nanofiber structure can increase electrode reaction active area, promote oxygen surface exchange and body diffusion rate, strengthen the oxygen reduction catalytic activity of negative electrode further, the combination property of low temperature solid-state oxide fuel battery cathode material in optimization.
2. two kinds of different component spinning precursor solutions are carried out electrostatic spinning, synchronously sinter phase into by a supplying method, obtain low temperature solid-state oxide fuel battery cathode in the nanofibrous structures be made up of nanofiber core and nanometer outer shell, nanofiber core and nanometer outer shell construct and are determined by the injection phase of two kinds of spinning precursor solutions, the thickness of fibronuclear diameter and outer shell is regulated and controled easily by the flow velocity changing spinning voltage and two kinds of spinning solutions, preparation technology is simple, and cost is lower.
Accompanying drawing explanation
Fig. 1 is a kind of electrostatic spinning schematic diagram.Component A spinning precursor solution and B component spinning precursor solution inject internal layer and outer layer channel respectively.
Fig. 2 is
as shown in Figure 1core-shell structure copolymer nanofiber side prepared by electrospinning device and cross section structure schematic diagram.Component A is as fiber core, and B component is as outer shell.
Fig. 3 is another kind of electrostatic spinning schematic diagram.Component A spinning precursor solution and B component spinning precursor solution inject skin and inner-layer channel respectively.
Fig. 4 is
as shown in Figure 3core-shell structure copolymer nanofiber side prepared by electrospinning device and cross section structure schematic diagram.Component A is as outer shell, and B component is as fiber core.
Embodiment
Be described further below by specific embodiment.
Electrospinning process is utilized to prepare by perovskite oxide PrBa
0.92co
2o
6-δ(δ is oxygen deficit) and electrolyte Gd
0.1ce
0.9o
1.95low temperature sofc cathode material in the core-shell structure copolymer nanofibrous structures formed
Step one, prepare PrBa respectively
0.92co
2o
6-δspinning precursor solution and Gd
0.1ce
0.9o
1.95spinning precursor solution
PrBa
0.92co
2o
6-δspinning precursor solution process for preparation:
According to synthesis 0.4mmol PrBa
0.92co
2o
6-δmetal ion metering than accurately taking Pr (NO
3)
36H
2o 0.174g, Ba (NO
3)
20.0961g, Co (Ac)
24H
2o 0.199g, puts into the mixed solvent be made up of 0.2ml deionized water, 0.5ml alcohol and 6ml DMF, and at room temperature magnetic agitation to above reagent dissolves completely, mixes; Then 1.0 grams of polyvinylpyrrolidones are dissolved in above mixed solution under magnetic stirring, obtain the PrBa mixed
0.92co
2o
6-δspinning precursor solution, by ultrasonic for the solution bubble that degass, at room temperature places 10 hours;
Electrolyte Gd
0.1ce
0.9o
1.95spinning precursor solution process for preparation:
Be dissolved in by 0.35 gram of polyvinylpyrrolidone in the mixed solvent be made up of 0.2ml deionized water, 0.5ml alcohol and 2ml DMF, at room temperature magnetic agitation is to dissolving completely; According to synthesis 0.4mmol Gd
0.1ce
0.9o
1.95metal ion metering than taking 0.156 gram of Ce (NO
3)
36H
2o, 0.018 gram of Gd (NO
3)
36H
2o, add in above mixed solution, room temperature lower magnetic force is stirred to and dissolves completely, obtains electrolyte Gd
0.1ce
0.9o
1.95spinning precursor solution, by ultrasonic for solution 2 bubble that degass, at room temperature places 10 hours.
Step 2, PrBa
0.92co
2o
6-δ-Gd
0.1ce
0.9o
1.95the electrostatic spinning preparation of core-shell structure copolymer nanofiber
The PrBa will prepared above respectively
0.92co
2o
6-δspinning precursor solution and Gd
0.1ce
0.9o
1.95spinning precursor solution injects the internal layer of electrostatic spinning syringe with in outer layer channel, and the spacing of adjustment spinning syringe needle and recipient is 10cm, and the 10-15 kV that adds high pressure coaxially sprays, and utilizes syringe pump control PrBa
0.92co
2o
6-δsolution and Gd
0.1ce
0.9o
1.95the flow velocity of solution is 5-20 μ l/min, and coaxial spinning obtains PrBa
0.92co
2o
6-δcomponent is fiber core, Gd
0.1ce
0.9o
1.9component is the nanofiber of outer shell; Change the injection phase of two kinds of spinning precursor solutions, by Gd
0.1ce
0.9o
1.95solution injects the inner-layer channel of electrostatic spinning syringe, and PrBa
0.92co
2o
6-δsolution injects outer layer channel, carries out electrostatic spinning, then obtains Gd
0.1ce
0.9o
1.9component is fiber core, PrBa
0.92co
2o
6-δcomponent is the concentric composite fibre of outer shell; By the PrBa obtained
0.92co
2o
6-δ-Gd
0.1ce
0.9o
1.95concentric composite fibre was 60 DEG C of drying box inner dryings process 20 hours.
Step 3, PrBa
0.92co
2o
6-δ-Gd
0.1ce
0.9o
1.95concentric composite fibre negative electrode sinters phase into
Will above dry rear PrBa
0.92co
2o
6-δ-Gd
0.1ce
0.9o
1.95concentric composite fibre carries out high temperature sintering, first be heated to 600 DEG C with 3 DEG C/min of heating rates, be incubated 3 hours, be then heated to 1050 DEG C with 5 DEG C/min of speed and be incubated 2 hours, finally be cooled to room temperature with 10 DEG C/min of speed, obtain two kinds of heteroid PrBa
0.92co
2o
6-δ-Gd
0.1ce
0.9o
1.95core-shell structure copolymer nanofiber cathode material, wherein PrBa
0.92co
2o
6-δfor orthorhombic phase laminated perovskite structure, Gd
0.1ce
0.9o
1.95for face-centered cubic phase structure.The PrBa obtained
0.92co
2o
6-δ-Gd
0.1ce
0.9o
1.95core-shell structure copolymer nanofiber negative electrode oxygen reduction catalytic activity at 500-700 DEG C of temperature strengthens 30-80%, and thermal coefficient of expansion reduces 20-40%, anti-CO
2adsorption poisons ability and improves 40-70%, and negative electrode combination property improves.
Claims (2)
1. low temperature solid-state oxide fuel battery cathode in a core-shell structure copolymer nanofibrous structures, it is characterized in that, described core-shell structure copolymer nanofibrous structures negative electrode is made up of nanofiber core and nanometer outer shell, described nanofiber core and nanometer outer shell are made up of perovskite structure ion-electron mixing conductor oxide component A and oxygen ion conductor electrolyte components B respectively, or it is contrary, form nanometer outer shell by perovskite structure ion-electron mixing conductor oxide component A, oxygen ion conductor electrolyte components B forms nanofiber core; In described nanofibrous structures, nanofiber nuclear diameter is 50-500 nanometer, and nanometer outer shell thickness is 100-800 nanometer.
2. the electrostatic spinning preparation method of low temperature solid-state oxide fuel battery cathode in a kind of core-shell structure copolymer nanofibrous structures according to claim 1, it is characterized in that, first respectively perovskite structure ion-electron mixing conductor oxide component A spinning precursor solution and oxygen ion conductor electrolyte components B spinning precursor solution is prepared, then two kinds of spinning precursor solutions are injected in internal layer and outer slinning cabinet respectively, or perovskite structure ion-electron mixing conductor oxide component A spinning precursor solution and oxygen ion conductor electrolyte components B spinning precursor solution are injected contrary slinning cabinet, carry out coaxial spinning, prepare concentric composite fibre, fiber drying, high temperature sintering, obtain the two kinds of different core-shell structure copolymer nanofibrous structures cathode materials be made up of perovskite structure ion-electron mixing conductor oxide component A and oxygen ion conductor electrolyte components B, 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, take the required acetate containing respective metal ion or nitrate reagent, deionization ethanol-water-N is dissolved under magnetic agitation, in dinethylformamide mixed solvent, then under magnetic stirring polyvinylpyrrolidone is dissolved in above mixed solution; Or, polyvinylpyrrolidone is dissolved in deionization ethanol-water-DMF mixed solvent first under magnetic stirring, and then by the required acetate containing respective metal ion or nitrate reagent adds, magnetic agitation is to dissolving completely; In mixed solution, the volume ratio of deionized water, alcohol and DMF solvent is 0.1-0.5:0.5-1: 5-10, and the consumption of polyvinylpyrrolidone is 1.5-3 times of acetate and nitrate reagent gross mass in above mixed solution; By the ultrasonic bubble that degass of perovskite structure oxide spinning precursor solution mixed, at room temperature place 5-15 hour;
Oxygen ion conductor electrolyte components B spinning precursor solution process for preparation:
According to the stoichiometric proportion of electrolyte oxide, take the required acetate containing respective metal ion or nitrate reagent, be dissolved in deionization ethanol-water-N under magnetic agitation, in dinethylformamide mixed solvent, then polyvinylpyrrolidone is dissolved in above mixed solution; Or, first polyvinylpyrrolidone is dissolved in deionization ethanol-water-DMF mixed solvent, and then by the required acetate containing respective metal ion or nitrate reagent adds, magnetic agitation is to dissolving completely; In mixed solution, the volume ratio of deionized water, alcohol and DMF solvent is 0.1-0.5:0.5-1: 5-10, and the consumption of polyvinylpyrrolidone is 1.5-3 times of acetate and nitrate reagent gross mass in above mixed solution; Obtain oxygen ion conductor electrolyte spinning precursor solution, by ultrasonic for solution 2 bubble that degass, at room temperature place 5-15 hour;
The electrostatic spinning preparation of step 2, core-shell structure copolymer nanofiber
In the internal layer respectively the perovskite structure ion-electron mixing conductor oxide component A spinning precursor solution for preparing above and oxygen ion conductor electrolyte components B spinning precursor solution being injected electrostatic spinning head and outer layer channel, carry out coaxial injection, spinning condition: the flow velocity 5-30 μ l/min of spinning solution, spinning voltage 10-25kV, the spacing 5-15cm of spinning syringe needle and recipient; The core-shell structure copolymer structure of nanofiber is determined in the injection phase of internal layer and outer layer channel by perovskite structure ion-electron mixing conductor oxide component A spinning precursor solution and oxygen ion conductor electrolyte components B spinning precursor solution, regulated and controled by the thickness of flow velocity to diameter fibronuclear in nanofiber and outer shell changing spinning voltage and two kinds of spinning solutions, obtain the concentric composite fibre of heteroid core-shell structure copolymer, then by fiber at 40-80 DEG C of drying box inner drying process 10-20 hour;
Step 3, core-shell structure copolymer nanofiber negative electrode sinter phase into
Above dry rear composite fibre is with one heart carried out high temperature sintering, sintering condition is: be heated to 400-600 DEG C with 3-6 DEG C/min of heating rate, insulation 2-5 hour, then be heated to 1000-1150 DEG C with 5-10 DEG C/min of speed and be incubated 1-5 hour, finally be cooled to room temperature with 5-12 DEG C/min of speed, in this high-temperature sintering process, perovskite structure oxide component respectively has phase of one's own with oxygen ion conductor electrolyte components, forms core-shell structure copolymer nanofiber cathode material.
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