CN102280646A - Method for preparing solid oxide fuel cell cathode material Rel+xA'1-xCuO4+/-Delta with one-dimensional nano-tubular structure by using electrospinning method - Google Patents

Method for preparing solid oxide fuel cell cathode material Rel+xA'1-xCuO4+/-Delta with one-dimensional nano-tubular structure by using electrospinning method Download PDF

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CN102280646A
CN102280646A CN2011101609371A CN201110160937A CN102280646A CN 102280646 A CN102280646 A CN 102280646A CN 2011101609371 A CN2011101609371 A CN 2011101609371A CN 201110160937 A CN201110160937 A CN 201110160937A CN 102280646 A CN102280646 A CN 102280646A
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孙丽萍
赵辉
王文学
李强
霍丽华
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Heilongjiang University
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Abstract

The invention provides a method for preparing a solid oxide fuel cell cathode material Rel+xA'1-xCuO4+/-Delta with a one-dimensional nano-tubular structure by using an electrospinning method, relating to a method for preparing the cell cathode material. The preparation method comprises the following steps of: stirring and mixing a precursor solution of Rel+xA'1-xCuO4+/-Delta and a polyvinylpyrrolidone ethanol solution, and standing to obtain a sol; placing the sol into an injector for spinning; then drying, and sintering twice to obtain the cell cathode material. The cell cathode material Rel+xA'1-xCuO4+/-Delta as an electrode has larger specific surface area such that an electrochemical reaction region is extended to the whole inside of a cathode, the number of reactivity sites is increased, and further the solid oxide fuel cell cathode material has the electrochemical property better than a powder electrode material.

Description

Method of electrostatic spinning preparation has the cathode material for solid-oxide fuel cell Re＜sub of 1-dimention nano tubular structure〉1+x＜/sub A '＜sub 1-x＜/sub CuO＜sub 4 ± δ＜/sub method
The method of electrostatic spinning preparation has the cathode material for solid-oxide fuel cell Re of 1-dimention nano tubular structure 1+xA ' 1-xCuO 4 ± δMethod
Technical field
The present invention relates to a kind of preparation method of battery cathode material.
Background technology
The practicability of Solid Oxide Fuel Cell need reduce operating temperature, to overcome the problems that face under the high temperature (as cell sealing, connector stability, material aging or the like).In order to realize this target, the electrode performance that improves existing cathode material is a key issue.The chemical property of negative electrode is not only with the structure of electrode material itself and form relevantly, and also microstructure and the pattern (such as grain size, porosity, electrode and electrolyte interface etc.) with electrode has close contact.Construct good negative electrode microstructure and can increase considerably phase reaction district area, improve the diffusion process of gas, and then improve the chemical property of negative electrode in electrode interior.K 2NiF 4Structure composite oxide has suitable thermal coefficient of expansion, can be preferably with CGO, LSGM etc. in the electrolyte of warm SOFC be complementary, in 600 ℃～800 ℃ mesophilic range, have the La of ratio 0.8Sr 0.2Co 0.4Fe 0.6O 3(LSCF) oxygen surface exchange performance that system is better and oxygen ions migrate ability, the research focus of the novel cathode material of warm SOFC in becoming.
Summary of the invention
The purpose of this invention is to provide a kind of cathode material for solid-oxide fuel cell Re with 1-dimention nano tubular structure 1+xA ' 1-xCuO 4 ± δThe preparation method.
Method of electrostatic spinning preparation of the present invention has the cathode material for solid-oxide fuel cell Re of 1-dimention nano tubular structure 1+xA ' 1-xCuO 4 ± δMethod as follows: one, polyvinylpyrrolidone is dissolved in behind the ethanol that the speed according to 30～80 rev/mins stirs 6h～8h under the condition of sealing, leave standstill 6h～12h then under the condition of room temperature, obtaining mass concentration is 9%～11% polyvinylpyrrolidone ethanolic solution; Two, according to chemical formula Re 1+xA ' 1-xCuO 4 ± δ, be (1+x) in the mol ratio of Re element, A ' element, Cu element and O element: (1-x): 1: (4 ± δ) ratio takes by weighing Re (NO respectively 3) 3, A ' (CH 3COO) 2And Cu (CH 3COO) 2, be dissolved in then in the distilled water, obtain the system 1 of homogeneous transparent, wherein Re 1+xA ' 1-xCuO 4 ± δQuality percentage composition in system 1 is 2%～8%, and wherein the Re element is a rare earth element, and A ' element is an alkali earth metal, chemical formula Re 1+xA ' 1-xCuO 4 ± δIn 0≤x≤1,0＜δ＜0.5; Three, the polyvinylpyrrolidone ethanolic solution that system 1 and step 1 are obtained mixes according to 1: 1 mass ratio, stirs 10h～12h with 30～80 rev/mins speed, leaves standstill 10h～12h then under the condition of room temperature, obtains colloidal sol; Four, colloidal sol is packed into pinhole aperture is in the syringe of 0.2mm～0.5mm, at the syringe pump flow velocity is that 1ml/h, voltage are 20kV, syringe needle tip and receive cylinder apart from being spinning 12h under the condition of 20cm, promptly get inorganic-organic precursor fiber, wherein syringe needle is connected with copper conductor, and copper conductor connects high voltage source; Five, inorganic-organic precursor fiber is dried 10h～14h under 50 ℃～80 ℃ condition, inorganic-organic precursor the fiber that to dry then is tiled in the alundum (Al porcelain boat in the Muffle furnace, speed according to 1 ℃/min rises to 350 ℃～500 ℃, sintering 2h～6h under 350 ℃～500 ℃ condition then, speed according to 1 ℃/min rises to 700 ℃～1000 ℃ again, sintering 15min～1h under 700 ℃～1000 ℃ condition promptly gets battery cathode material Re then 1+xA ' 1-xCuO 4 ± δRe element described in the step 2 is La, Ce, Pr, Nd, Sm, Gd, Dy or Eu; A ' element described in the step 2 is Ca, Sr or Ba.
The present invention utilizes electrostatic spinning technique to develop new one-dimensional tubulose K 2NiF 4Warm oxide fuel battery cathode material Re in the structure 1+xA ' 1-xCuO 4 ± δ, make it have at middle low-temperature space that (mixed conductivity of material is near 100Scm in 750 ℃ of air than higher oxonium ion-electronics mixed conductivity -1), better chemical stability (under 1000 ℃ of air atmospheres 24 hours materials of sintering not with CGO electrolyte generation chemical reaction) and thermal stability are arranged simultaneously.Battery cathode material Re of the present invention 1+xA ' 1-xCuO 4 ± δThe one dimension tubular structure make it have bigger specific area as electrode, make the electrochemical reaction district expand to whole negative electrode inside, increased the reactivity number of loci, thereby had the chemical property that is better than the powder electrode material.
The present invention is by the Prepared by Sol Gel Method precursor sol, and control spinning and postorder heat-treat condition can obtain the Nano tube of composite oxides that uniform diameter is 100nm～200nm, and this class material is 10 in partial pressure of oxygen -5To the 0.2atm scope, show very high oxonium ion-electronics mixed conductivity, and its oxygen ionic conductivity is (under 800 ℃ of air greater than 0.06Scm -1) (oxygen ionic conductivity as LSCF is about 0.03Scm under 800 ℃ to be higher than the cathode material of perovskite structure -1).Battery cathode material Re with the present invention's preparation 1+xA ' 1-xCuO 4 ± δBe negative electrode, reveal good heat, chemical stability and oxygen catalytic reduction character at material list below 800 ℃.This class material coefficient of thermal expansion coefficient (13 * 10 -6Cm/cm ℃～14 * 10 -6Cm/cm ℃) approaching with the CGO material, the cathode material that is suitable as Solid Oxide Fuel Cell uses.
Description of drawings
Fig. 1 is embodiment 16 gained La 2CuO 4Nanotube chemical stability XRD testing result figure, a represents the XRD curve of CGO powder among the figure, b represents La 2CuO 4The XRD curve of nanotube, c represents La 2CuO 4The XRD curve of 1000 ℃ of sintering of nanotube and CGO powder after 24 hours, ■ represents La 2CuO 4Nanotube, * are represented the CGO powder; Fig. 2 is 0.5 hour rear electrode surface topography map of 900 ℃ of sintering in the embodiment 16; Fig. 3 is embodiment 16 gained La 2CuO 4Nanotube, CGO and LSCF material coefficient of thermal expansion coefficient survey map, among the figure-■-expression La 2CuO 4The thermal coefficient of expansion of nanotube,
Figure BDA0000068554650000021
The thermal coefficient of expansion of expression CGO, the thermal coefficient of expansion of-★-expression LSCF; Fig. 4 is embodiment 16 gained La 2CuO 4Nanotube and embodiment 17 gained La 1+xSr 1-xCuO 4Dc conductivity test result figure, among the figure
Figure BDA0000068554650000022
Expression La 2CuO 4The dc conductivity test result of nanotube,
Figure BDA0000068554650000023
Expression La 1.9Sr 0.1CuO 4The dc conductivity test result,
Figure BDA0000068554650000024
Expression La 1.7Sr 0.3CuO 4The dc conductivity test result, ■ represents La 1.5Sr 0.5CuO 4The dc conductivity test result; Fig. 5 is embodiment 16 La in air 2CuO 4Powder and La 2CuO 4The polarization resistance of nanotube electrode varies with temperature graph of a relation, and ■ represents La among the figure 2CuO 4Powder polarization of electrode resistance varies with temperature graph of a relation,
Figure BDA0000068554650000031
Expression embodiment 16 gained La 2CuO 4The polarization resistance of nanotube electrode varies with temperature graph of a relation; Fig. 6 be embodiment 16 step 4 gained inorganic-image of organic precursor fiber; Fig. 7 is gained La in the embodiment 16 2CuO 4The SEM image of nanotube; Fig. 8 is gained La in the embodiment 16 2CuO 4The TEM image of nanotube.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the combination in any between each embodiment.
Embodiment one: the method for electrostatic spinning preparation has the cathode material for solid-oxide fuel cell Re of 1-dimention nano tubular structure in the present embodiment 1+xA ' 1-xCuO 4 ± δMethod as follows: one, polyvinylpyrrolidone is dissolved in behind the ethanol that the speed according to 30～80 rev/mins stirs 6h～8h under the condition of sealing, leave standstill 6h～12h then under the condition of room temperature, obtaining mass concentration is 9%～11% polyvinylpyrrolidone ethanolic solution; Two, according to chemical formula Re 1+xA ' 1-xCuO 4 ± δ, be (1+x) in the mol ratio of Re element, A ' element, Cu element and O element: (1-x): 1: (4 ± δ) ratio takes by weighing Re (NO respectively 3) 3, A ' (CH 3COO) 2And Cu (CH 3COO) 2, be dissolved in then in the distilled water, obtain the system 1 of homogeneous transparent, wherein Re 1+xA ' 1-xCuO 4 ± δQuality percentage composition in system 1 is 2%～8%, and wherein the Re element is a rare earth element, and A ' element is an alkali earth metal, chemical formula Re 1+xA ' 1-xCuO 4 ± δIn 0≤x≤1,0＜δ＜0.5; Three, the polyvinylpyrrolidone ethanolic solution that system 1 and step 1 are obtained mixes according to 1: 1 mass ratio, stirs 10h～12h with 30～80 rev/mins speed, leaves standstill 10h～12h then under the condition of room temperature, obtains colloidal sol; Four, colloidal sol is packed into pinhole aperture is in the syringe of 0.2mm～0.5mm, at the syringe pump flow velocity is that 1ml/h, voltage are 20kV, syringe needle tip and receive cylinder apart from being spinning 12h under the condition of 20cm, promptly get inorganic-organic precursor fiber, wherein syringe needle is connected with copper conductor, and copper conductor connects high voltage source; Five, inorganic-organic precursor fiber is dried 10h～14h under 50 ℃～80 ℃ condition, inorganic-organic precursor the fiber that to dry then is tiled in the alundum (Al porcelain boat in the Muffle furnace, speed according to 1 ℃/min rises to 350 ℃～500 ℃, sintering 2h～6h under 350 ℃～500 ℃ condition then, speed according to 1 ℃/min rises to 700 ℃～1000 ℃ again, sintering 15min～1h under 700 ℃～1000 ℃ condition promptly gets battery cathode material Re then 1+xA ' 1-xCuO 4 ± δRe element described in the step 2 is La, Ce, Pr, Nd, Sm, Gd, Dy or Eu; A ' element described in the step 2 is Ca, Sr or Ba.
The average diameter of the inorganic-organic precursor fiber that obtains in the present embodiment step 4 is about 500nm.The battery cathode material Re that present embodiment obtains 1+xA ' 1-xCuO 4 ± δBe that homogeneous diameter is the Nano tube of composite oxides of 100nm～200nm.
The mass concentration of polyvinylpyrrolidone ethanolic solution is necessary for 9%～11% in the present embodiment step 1, the mass concentration of polyvinylpyrrolidone is less than 9% or all can not get nano tube structure greater than 11%, can access nano belt or solid nanometer necklace less than 9%, form solid nano belt greater than 11%; This is because when polyvinylpyrrolidone content (less than 9%) more after a little while, and inorganic salts are tending towards reuniting in heat treatment process, form island structure in precursor fibre, and then polyvinylpyrrolidone is removed the back inorganic particulate and linked to each other and form the nanometer necklace; When polyvinylpyrrolidone is too much (greater than 11%), increase with polyvinylpyrrolidone content, solid content is big in the precursor fibre, in electric field, stretched by electric field force, formed flaky texture, because quick volatilization, the solid content of solvent are big, final getting so that this banded structure keeps getting off.In suitable polyvinylpyrrolidone content range, because capillary its surface compressed effect forms column, in heat treatment process, softening and the decomposition of polyvinylpyrrolidone is carried out simultaneously, form phase-separated state with inorganic salts, polyvinylpyrrolidone raises to decompose with temperature and forms nano tubular structure afterwards.
Re in the present embodiment step 2 1+xA ' 1-xCuO 4 ± δConcentration in system 1 is one of key factor of regulation and control nano tube structure, Re 1+xA ' 1-xCuO 4 ± δConcentration in system 1 is lower than 2% and forms solid nanometer necklace, Re 1+xA ' 1-xCuO 4 ± δConcentration in system 1 is higher than 8% and forms nanofiber; Control sintering temperature and sintering time are one of key factors that keeps the nanotube pattern in the step 5, but the longest sintering 1h in the time of 700 ℃, and maximum sintering 15min 1000 ℃ the time, temperature surpasses 1000 ℃ or the long nanotube pattern that all can make of sintering time caves in, and forms solid nanofiber at last.
Present embodiment is raw materials used all available from Beijing chemical reagents corporation.
Present embodiment is by the Prepared by Sol Gel Method precursor sol, and control spinning and postorder heat-treat condition can obtain the Nano tube of composite oxides that uniform diameter is 100nm～200nm, and this class material is 10 in partial pressure of oxygen -5To the 0.2atm scope, show very high oxonium ion-electronics mixed conductivity, and its oxygen ionic conductivity is (under 800 ℃ of air greater than 0.06Scm -1) (oxygen ionic conductivity as LSCF is about 0.03Scm under 800 ℃ to be higher than the cathode material of perovskite structure -1).Battery cathode material Re with the present invention's preparation 1+xA ' 1-xCuO 4 ± δBe negative electrode, reveal good heat, chemical stability and oxygen catalytic reduction character at material list below 800 ℃.This class material coefficient of thermal expansion coefficient (13 * 10 -6Cm/cm ℃～14 * 10 -6Cm/cm ℃) approaching with the CGO material, the cathode material that is suitable as Solid Oxide Fuel Cell uses.
Embodiment two: present embodiment and embodiment one are different is that the mass concentration of the ethanolic solution of polyvinylpyrrolidone described in the step 1 is 10%.Other is identical with embodiment one.
Embodiment three: that present embodiment is different with one of embodiment one or two is Re in the step 2 1+xA ' 1-xCuO 4 ± δQuality percentage composition in system 1 is 3%～7%.Other is identical with one of embodiment one or two.
Embodiment four: that present embodiment and embodiment three are different is Re in the step 2 1+xA ' 1-xCuO 4 ± δQuality percentage composition in system 1 is 5%.Other is identical with embodiment three.
Embodiment five: present embodiment is different with one of embodiment one to four is that the pinhole aperture of in the step 4 colloidal sol being packed into is in the syringe of 0.3mm.Other is identical with one of embodiment one to four.
Embodiment six: what present embodiment was different with one of embodiment one to four is in the step 5 inorganic-organic precursor fiber to be dried under 60 ℃～70 ℃ condition.Other is identical with one of embodiment one to four.
Embodiment seven: what present embodiment was different with one of embodiment one to four is in the step 5 inorganic-organic precursor fiber to be dried under 65 ℃ condition.Other is identical with one of embodiment one to four.
Embodiment eight: present embodiment is different with one of embodiment one to four be in the step 5 under 400 ℃ condition sintering 4h, sintering 45min under 900 ℃ condition again.Other is identical with one of embodiment one to four.
Embodiment nine: what present embodiment was different with one of embodiment one to four is that the speed according to 40～70 rev/mins stirs in the step 1.Other is identical with one of embodiment one to four.
Embodiment ten: what present embodiment was different with one of embodiment one to four is that the speed according to 50～60 rev/mins stirs in the step 1.Other is identical with one of embodiment one to four.
Embodiment 11: what present embodiment was different with one of embodiment one to four is that the speed according to 55 rev/mins stirs in the step 1.Other is identical with one of embodiment one to four.
Embodiment 12: what present embodiment was different with one of embodiment one to four is to leave standstill 7h～11h in the step 1 under the condition of room temperature.Other is identical with one of embodiment one to four.
Embodiment 13: what present embodiment was different with one of embodiment one to four is to leave standstill 8h～10h in the step 1 under the condition of room temperature.Other is identical with one of embodiment one to four.
Embodiment 14: what present embodiment was different with one of embodiment one to four is to leave standstill 9h in the step 1 under the condition of room temperature.Other is identical with one of embodiment one to four.
Embodiment 15: that present embodiment is different with one of embodiment one to four is mixing time 7h in the step 1.Other is identical with one of embodiment one to four.
Embodiment 16: the method for electrostatic spinning preparation has the cathode material for solid-oxide fuel cell La of 1-dimention nano tubular structure in the present embodiment 2CuO 4Method as follows: one, polyvinylpyrrolidone is dissolved in behind the ethanol that the speed according to 30 rev/mins stirs 7h under the condition of sealing, leaves standstill 6h then under the condition of room temperature, obtaining mass concentration is 9% polyvinylpyrrolidone ethanolic solution; Two, according to chemical formula La 2CuO 4, be that 2: 1: 4 ratio takes by weighing La (NO respectively in the mol ratio of La element, Cu element and O element 3) 3And Cu (CH 3COO) 2, be dissolved in then in the distilled water, obtain the system 1 of homogeneous transparent, wherein La 2CuO 4Quality percentage composition in system 1 is 2%; Three, the polyvinylpyrrolidone ethanolic solution that system 1 and step 1 are obtained mixes according to 1: 1 mass ratio, stirs 11h with 50 rev/mins speed, leaves standstill 11h then under the condition of room temperature, obtains colloidal sol; Four, colloidal sol is packed into pinhole aperture is in the syringe of 0.4mm, at the syringe pump flow velocity is that 1ml/h, voltage are 20kV, syringe needle tip and receive cylinder apart from being spinning 12h under the condition of 20cm, promptly get inorganic-organic precursor fiber, wherein syringe needle is connected with copper conductor, and copper conductor connects high voltage source; Five, inorganic-organic precursor fiber is dried 12h under 60 ℃ condition, inorganic-organic precursor the fiber that to dry then is tiled in the alundum (Al porcelain boat in the Muffle furnace, speed according to 1 ℃/min rises to 400 ℃, sintering 4h under 400 ℃ condition then, speed according to 1 ℃/min rises to 900 ℃ again, sintering 0.5h under 900 ℃ condition promptly gets battery cathode material La then 2CuO 4Nanotube.
The average diameter of the inorganic-organic precursor fiber that obtains in the present embodiment step 4 is about 500nm, gained battery cathode material La 2CuO 4Nanotube is that diameter is the single-phase K of 100nm～200nm 2NiF 4The structure nano tube material.
La with the present embodiment preparation 2CuO 4Nanotube mixes according to 1: 1 weight ratio with the CGO powder, grinds 24 hours (make wetting agent with ethanol, do abrasive material with the zirconium oxide microballoons that diameter is about 1 millimeter) in ball mill, forms homogeneous mixture.Then mixture is taken out,,, take out grind into powder once more,, find out the battery cathode material La of present embodiment by Fig. 1 with XRD check thing phase 1000 ℃ of following continuous sinterings 24 hours at the 100MPa lower sheeting 2CuO 4Nanotube under 1000 ℃ of air atmospheres 24 hours materials of sintering not with CGO electrolyte generation chemical reaction (referring to Fig. 1 c);
La with the present embodiment preparation 2CuO 4Nanotube grinds to form short nanotube with mortar, and short nanotube and the terpinol of collecting restrained La according to 1 2CuO 4Nanotube adds the mixed of 1 milliliter of terpinol, forms prepared Chinese ink shape mixture.Getting above-mentioned prepared Chinese ink shape mixture drips on CGO potsherd one side surface of crossing with 80 orders and 200 order liquid honings in advance (every about 0.03 milliliter), obtain cathode with spin-coating method with 100 rev/mins rotating speed, it was placed 24 hours in 150 ℃ of baking ovens, then as in the high temperature box furnace, first sintering 2 hours under 500 ℃ of air atmospheres, sintering 0.5 hour under 900 ℃ of air atmospheres forms negative electrode/electrolyte assembly then.Anode and reference electrode make with platinum slurry (available from the expensive platinum industry of grinding).Platinum slurry is coated with invests electrolytical opposite side, then at 850 ℃ of following sintering 0.5h, form anode and reference electrode 500 ℃ of following sintering 4 hours.Observe the cathode surface pattern with SEM.Observed result shows that negative electrode has equally distributed crossover network structure (referring to Fig. 2).
La with the present embodiment preparation 2CuO 4Nanotube grinds to form short nanotube with mortar, with the short nanotube collected at the 100MPa lower sheeting, 1000 ℃ of following continuous sinterings 24 hours; Take out grind into powder once more,,, obtain La 1000 ℃ of following continuous sinterings 24 hours at the 300MPa lower sheeting 2CuO 4Potsherd.With 200 order sand paper the sample two sides is polished, polishes.Utilize the SETSYS Evolution TMA test macro of French Setaram company to measure thermal coefficient of expansion.Test condition: work atmosphere is an air, and temperature-measuring range is 100 ℃～900 ℃, and heating rate is 5 ℃/min.The result who obtains shows, La 2CuO 4Thermal coefficient of expansion be 13.2 * 10 -6Cm/cm ℃, the thermal coefficient of expansion of CGO is 13.1 * 10 -6Cm/cm ℃, and the thermal coefficient of expansion of LSCF is 15 * 10 -6Cm/cm ℃～17 * 10 -6Cm/cm ℃ (referring to Fig. 3).La by contrast 2CuO 4Thermal coefficient of expansion near CGO, indicating with La 2CuO 4The interface of doing negative electrode and CGO formation has thermal shock resistance preferably.
The La that adopts direct current four electrode methods test present embodiment to obtain 2CuO 4The mixed conductivity of potsherd, platinum is done electrode.Test atmosphere is air.The result shows La 2CuO 4Mixed conductivity reach 16Scm at 750 ℃ -1(referring to Fig. 4).
Adopt the complex impedance measuring technology, measure cathodic polarization resistance by making up three-electrode system.Test result shows, La 2CuO 4The polarization resistance value (ASR) that nanotube electrode measures in 750 ℃ of air is 0.43Scm -1, be better than La 2CuO 4(value under the same test condition is approximately 0.78Scm to powder body material -1) (referring to Fig. 5).
Embodiment 17: the method for electrostatic spinning preparation has the cathode material for solid-oxide fuel cell La of 1-dimention nano tubular structure in the present embodiment 1+xSr 1-xCuO 4Method as follows: one, polyvinylpyrrolidone is dissolved in behind the ethanol that the speed according to 30 rev/mins stirs 7h under the condition of sealing, leaves standstill 6h then under the condition of room temperature, obtaining mass concentration is 9% polyvinylpyrrolidone ethanolic solution; Two, according to chemical formula La 1+xSr 1-xCuO 4, be (1.5～1.9) in the mol ratio of La element, Sr element, Cu element and O element: (0.1～0.5): 1: 4 ratio takes by weighing La (NO respectively 3) 3, Sr (CH 3COO) 2And Cu (CH 3COO) 2, be dissolved in then in the distilled water, obtain the system 1 of homogeneous transparent, wherein La 1+xSr 1-xCuO 4Quality percentage composition in system 1 is 2%; Three, the polyvinylpyrrolidone ethanolic solution that system 1 and step 1 are obtained mixes according to 1: 1 mass ratio, stirs 11h with 50 rev/mins speed, leaves standstill 11h then under the condition of room temperature, obtains colloidal sol; Four, colloidal sol is packed into pinhole aperture is in the syringe of 0.4mm, at the syringe pump flow velocity is that 1ml/h, voltage are 20kV, syringe needle tip and receive cylinder apart from being spinning 12h under the condition of 20cm, promptly get inorganic-organic precursor fiber, wherein syringe needle is connected with copper conductor, and copper conductor connects high voltage source; Five, inorganic-organic precursor fiber is dried 12h under 60 ℃ condition, inorganic-organic precursor the fiber that to dry then is tiled in the alundum (Al porcelain boat in the Muffle furnace, speed according to 1 ℃/min rises to 400 ℃, sintering 4h under 400 ℃ condition then, speed according to 1 ℃/min rises to 900 ℃ again, sintering 0.5h under 900 ℃ condition promptly gets battery cathode material La then 1+xSr 1-xCuO 4
La as shown in Figure 4 1+xSr 1-xCuO 4Mixed conductivity under 750 ℃ of air atmospheres, change with change of component, its conductivity value is at 16Scm -1～130Scm -1Between, all reach the requirement of cathode material.

Claims (8)

1. the method for electrostatic spinning preparation has the cathode material for solid-oxide fuel cell Re of 1-dimention nano tubular structure 1+xA ' 1-xCuO 4 ± δMethod, it is characterized in that method of electrostatic spinning preparation has the cathode material for solid-oxide fuel cell Re of 1-dimention nano tubular structure 1+xA ' 1-xCuO 4 ± δMethod as follows: one, polyvinylpyrrolidone is dissolved in behind the ethanol that the speed according to 30～80 rev/mins stirs 6h～8h under the condition of sealing, leave standstill 6h～12h then under the condition of room temperature, obtaining mass concentration is 9%～11% polyvinylpyrrolidone ethanolic solution; Two, according to chemical formula Re 1+xA ' 1-xCuO 4 ± δ, be (1+x) in the mol ratio of Re element, A ' element, Cu element and O element: (1-x): 1: (4 ± δ) ratio takes by weighing Re (NO respectively 3) 3, A ' (CH 3COO) 2And Cu (CH 3COO) 2, be dissolved in then in the distilled water, obtain the system 1 of homogeneous transparent, wherein Re 1+xA ' 1-xCuO 4 ± δQuality percentage composition in system 1 is 2%～8%, and wherein the Re element is a rare earth element, and A ' element is an alkali earth metal, chemical formula Re 1+xA ' 1-xCuO 4 ± δIn 0≤x≤1,0＜δ＜0.5; Three, the polyvinylpyrrolidone ethanolic solution that system 1 and step 1 are obtained mixes according to 1: 1 mass ratio, stirs 10h～12h with 30～80 rev/mins speed, leaves standstill 10h～12h then under the condition of room temperature, obtains colloidal sol; Four, colloidal sol is packed into pinhole aperture is in the syringe of 0.2mm～0.5mm, at the syringe pump flow velocity is that 1ml/h, voltage are 20kV, syringe needle tip and receive cylinder apart from being spinning 12h under the condition of 20cm, promptly get inorganic-organic precursor fiber, wherein syringe needle is connected with copper conductor, and copper conductor connects high voltage source; Five, inorganic-organic precursor fiber is dried 10h～14h under 50 ℃～80 ℃ condition, inorganic-organic precursor the fiber that to dry then is tiled in the alundum (Al porcelain boat in the Muffle furnace, speed according to 1 ℃/min rises to 350 ℃～500 ℃, sintering 2h～6h under 350 ℃～500 ℃ condition then, speed according to 1 ℃/min rises to 700 ℃～1000 ℃ again, sintering 15min～1h under 700 ℃～1000 ℃ condition promptly gets battery cathode material Re then 1+xA ' 1-xCuO 4 ± δRe element described in the step 2 is La, Ce, Pr, Nd, Sm, Gd, Dy or Eu; A ' element described in the step 2 is Ca, Sr or Ba.
2. prepare cathode material for solid-oxide fuel cell Re according to the described method of electrostatic spinning of claim 1 with 1-dimention nano tubular structure 1+xA ' 1-xCuO 4 ± δMethod, the mass concentration that it is characterized in that the ethanolic solution of polyvinylpyrrolidone described in the step 1 is 10%.
3. prepare cathode material for solid-oxide fuel cell Re according to claim 1 or 2 described method of electrostatic spinning with 1-dimention nano tubular structure 1+xA ' 1-xCuO 4 ± δMethod, it is characterized in that Re in the step 2 1+xA ' 1-xCuO 4 ± δQuality percentage composition in system 1 is 3%～7%.
4. prepare cathode material for solid-oxide fuel cell Re according to the described method of electrostatic spinning of claim 3 with 1-dimention nano tubular structure 1+xA ' 1-xCuO 4 ± δMethod, it is characterized in that Re in the step 2 1+xA ' 1-xCuO 4 ± δQuality percentage composition in system 1 is 5%.
5. prepare cathode material for solid-oxide fuel cell Re according to the described method of electrostatic spinning of claim 3 with 1-dimention nano tubular structure 1+xA ' 1-xCuO 4 ± δMethod, the pinhole aperture that it is characterized in that in the step 4 colloidal sol packed into is in the syringe of 0.3mm.
6. prepare cathode material for solid-oxide fuel cell Re according to the described method of electrostatic spinning of claim 3 with 1-dimention nano tubular structure 1+xA ' 1-xCuO 4 ± δMethod, it is characterized in that in the step 5 inorganic-organic precursor fiber being dried under 60 ℃～70 ℃ condition.
7. prepare cathode material for solid-oxide fuel cell Re according to the described method of electrostatic spinning of claim 3 with 1-dimention nano tubular structure 1+xA ' 1-xCuO 4 ± δMethod, it is characterized in that in the step 5 inorganic-organic precursor fiber being dried under 65 ℃ condition.
8. prepare cathode material for solid-oxide fuel cell Re according to the described method of electrostatic spinning of claim 3 with 1-dimention nano tubular structure 1+xA ' 1-xCuO 4 ± δMethod, it is characterized in that in the step 5 sintering 4h, sintering 45min under 900 ℃ condition again under 400 ℃ condition.
CN2011101609371A 2011-06-15 2011-06-15 Method for preparing solid oxide fuel cell cathode material Rel+xA'1-xCuO4+/-Delta with one-dimensional nano-tubular structure by using electrospinning method Pending CN102280646A (en)

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CN103531825A (en) * 2013-10-25 2014-01-22 哈尔滨工业大学 Method for effectively enlarging surface area of micro-nano electrode particle
CN107660318A (en) * 2015-06-30 2018-02-02 株式会社Lg化学 Manufacture method, electrolyte for solid oxide fuel cell film, SOFC and the fuel cell module of electrolyte for solid oxide fuel cell film

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Publication number Priority date Publication date Assignee Title
CN103531825A (en) * 2013-10-25 2014-01-22 哈尔滨工业大学 Method for effectively enlarging surface area of micro-nano electrode particle
CN107660318A (en) * 2015-06-30 2018-02-02 株式会社Lg化学 Manufacture method, electrolyte for solid oxide fuel cell film, SOFC and the fuel cell module of electrolyte for solid oxide fuel cell film
CN107660318B (en) * 2015-06-30 2021-05-11 株式会社Lg化学 Method for producing electrolyte membrane for solid oxide fuel cell, and fuel cell module

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