CN101572315B - Method for preparing battery cathode material Re<2-x>A'<x>CuO<4 delta> with K<2>NiF<4> structure using electrostatic spinning method - Google Patents
Method for preparing battery cathode material Re<2-x>A'<x>CuO<4 delta> with K<2>NiF<4> structure using electrostatic spinning method Download PDFInfo
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- CN101572315B CN101572315B CN2009100722007A CN200910072200A CN101572315B CN 101572315 B CN101572315 B CN 101572315B CN 2009100722007 A CN2009100722007 A CN 2009100722007A CN 200910072200 A CN200910072200 A CN 200910072200A CN 101572315 B CN101572315 B CN 101572315B
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Abstract
The invention provides a method for preparing catelectrode material Ln<2-x>A'<x>CuO<4+/-delta> with a K2NiF4 structure by electrostatic spinning, which relates to a method for preparing the catelectrode material. The invention solves the problems of poor chemical stability and poor electrode performance of the existing catelectrode material. The method is as follows: a precursor solution of Ln<2-x>A'<x>CuO<4+/-delta> and an ethanol solution of polyvinylpyrrolidone are stirred and mixed to stand still; obtained collosol is filled in a syringe, is spun for 6h under the injector pump conditions of 5m1/h flow rate and 30 kV voltage, and then is dried to be treated by double sintering so as to obtain the catelectrode material Ln<2-x>A'<x>CuO<4+/-delta>.The catelectrode material Ln<2-x>A'<x>CuO<4+/-delta> obtained in the invention is fibrous, and the diameter is 200 to 350nm; the value of polarization resistance is low, and the value of specific conductivity is 10 to 40 Scm<-1>; cathodic polarization overpotential is less than Sr<0.5>Sm<1.5>NiO4 and La0.8Sr0.2Co0.4Fe0.6O3.
Description
Technical field
The present invention relates to a kind of preparation method of battery cathode material.
Background technology
Intermediate temperature solid oxide fuel cell (ITSOFC) is a kind of efficient, eco-friendly electrical energy production mode.Yet the reduction of battery operational temperatures causes the rapid decline of electrode activity, and the performance impact of cathode material the performance quality of entire cell system.La
0.8Sr
0.2Co
0.4Fe
0.6O
3Oxygen ionic conductivity is about 0.03Scm under the condition of 800 ℃ of temperature
-1, temperature is that 700 ℃, current density are 56mAcm
-2Condition under Sr
0.5Sm
1.5NiO
4The cathodic polarization electromotive force is greater than 150mV, and temperature is that 800 ℃, current density are 20mAcm
-2Condition under La
0.85Sr
0.15MnO
3The cathodic polarization electromotive force be 205mV, see that thus the poor chemical stability, the electrode performance that have cathode material are poor.
Summary of the invention
Technical problem to be solved by this invention is for the poor chemical stability that solves existing cathode material, the problem of electrode performance difference, provides a kind of method of electrostatic spinning preparation to have K
2NiF
4The battery cathode material Re of structure
2-xA '
xCuO
4 ± δMethod.
Method of electrostatic spinning preparation of the present invention has K
2NiF
4The battery cathode material Re of structure
2-xA '
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 8%～15% polyvinylpyrrolidone ethanolic solution; Two, according to chemical formula Re
2-xA '
xCuO
4 ± δ, be (2-x): x in the mol ratio of Re element, A ' element, Cu element and O element: 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
2-xA '
xCuO
4 ± δQuality percentage composition in system 1 is 8%～20%, and the Re element is a rare earth element, and A ' element is an alkali earth metal, chemical formula Re
2-xA '
xCuO
4 ± δIn 0.01＜x＜1,0＜δ＜0.5; Three, the polyvinylpyrrolidone ethanolic solution that system 1 and step 1 are obtained is according to 2～4: 1 mass ratio mixes, stir 10h～12h with 30～80 rev/mins speed, under the condition of room temperature, leave standstill 10h～12h then, obtain colloidal sol: four, with the colloidal sol pinhole aperture of packing into is in the syringe of 0.8mm～1.5mm, at the syringe pump flow velocity is 5ml/h, voltage is 30kV, syringe needle most advanced and sophisticated with receive spinning 6h under the condition that the cylinder distance is 25cm, 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 70 ℃～90 ℃ 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 2 ℃/min rises to 350 ℃～500 ℃, sintering 2h～6h under 350 ℃～500 ℃ condition then, speed according to 2 ℃/min rises to 700 ℃～1000 ℃ again, sintering 10～14h under 700～1000 ℃ condition promptly gets battery cathode material Re then
2-xA '
xCuO
4 ± δ
The battery cathode material Re of gained of the present invention
2-xA '
xCuO
4 ± δFor fibrous, diameter is about 200～350nm, with Re
2-xA '
xCuO
4 ± δPowder body material is compared the battery cathode material Re of gained of the present invention
2-xA '
xCuO
4 ± δThe polarization resistance value little, conductivity value is 10-40Scm
-1, having reached intermediate temperature solid oxide fuel cell cathode material hybrid conductive rate is 10Scm
-1Above requirement can be used as cathode material; Under the same test condition, the battery cathode material Re of gained of the present invention
2-xA '
xCuO
4 ± δThe cathodic polarization electromotive force all less than Sr
0.5Sm
1.5NiO
4And La
0.8Sr
0.2Co
0.4Fe
0.6O
3, performance is better than Sr
0.5Sm
1.5NiO
4And La
0.85Sr
0.15MnO
3, and the battery cathode material Re of gained of the present invention
2-xA '
xCuO
4 ± δThermal coefficient of expansion near Cd
0.1Ce
0.9O
2Thermal coefficient of expansion, adopt the battery cathode material Re of gained of the present invention
2-xA '
xCuO
4 ± δBe negative electrode and Cd
0.1Ce
0.9O
2The interface that forms can have thermal shock resistance preferably.
Description of drawings
Fig. 1 is gained battery cathode material Nd in the embodiment 20
1.93Sr
0.07CuO
4Stereoscan photograph.Fig. 2 is that cathodic polarization resistance varies with temperature figure in the embodiment 20, and ■ represents gained Nd in the embodiment 20
1.93Sr
0.07CuO
4Cathodic polarization resistance vary with temperature figure, zero the expression Nd
1.93Sr
0.07CuO
4Powder cathodic polarization resistance varies with temperature figure.Fig. 3 is a battery cathode material work polarization curve comparison diagram in the embodiment 20, and ■ represents La
0.85Sr
0.15MnO
3As battery cathode material work polarization curve, ◇ represents Sr
0.5Sm
1.5NiO
4As battery cathode material work polarization curve, ★ represents Nd
1.93Sr
0.07CuO
4As battery cathode material work polarization curve.Fig. 4 is the XRD figure spectrum in the embodiment 20, and a represents Cd
0.1Ce
0.9O
2The XRD curve of powder; B represents Nd
1.93Sr
0.07CuO
4XRD curve c: the expression Nd
1.93Sr
0.07CuO
4With Cd
0.1Ce
0.9O
2Mixture is at the XRD curve of 1000 degree sintering after 24 hours.Fig. 5 is the gained cathode surface shape appearance figure in the embodiment 20.Fig. 6 is a gained thermal coefficient of expansion comparison diagram in the embodiment 20 ,-■-expression Nd
1.93Sr
0.07CuO
4The thermal coefficient of expansion curve,
Expression Cd
0.1Ce
0.9O
2The thermal coefficient of expansion curve ,-★-expression La
0.8Sr
0.2Co
0.4Fe
0.6O
3The thermal coefficient of expansion curve.Fig. 7 is a mixed conductivity comparison diagram in the embodiment 20,
Expression activation energy is the Nd of 0.60ev
2CuO
4The mixed conductivity curve,
Expression activation energy is the Nd of 0.47ev
1.95Sr
0.05CuO
4The mixed conductivity curve, ★ represents that activation energy is the Nd of 0.73ev
1.93Sr
0.07CuO
4The mixed conductivity curve,
Expression activation energy is the Nd of 0.85ev
1.9Sr
0.1CuO
4The mixed conductivity curve.
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 K in the present embodiment
2NiF
4The battery cathode material Re of structure
2-xA '
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 8%～15% polyvinylpyrrolidone ethanolic solution; Two, according to chemical formula Re
2-xA '
xCuO
4 ± δ, be (2-x): x in the mol ratio of Re element, A ' element, Cu element and O element: 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
2-xA '
xCuO
4 ± δQuality percentage composition in system 1 is 8%～20%, and the Re element is a rare earth element, and A ' element is an alkali earth metal, chemical formula Re
2-xA '
xCuO
4 ± δIn 0.01＜x＜1,0＜δ＜0.5; Three, the polyvinylpyrrolidone ethanolic solution that system 1 and step 1 are obtained is according to 2～4: 1 mass ratio mixes, stir 10h～12h with 30～80 rev/mins speed, under the condition of room temperature, leave standstill 10h～12h then, obtain colloidal sol: four, with the colloidal sol pinhole aperture of packing into is in the syringe of 0.8mm～1.5mm, at the syringe pump flow velocity is 5ml/h, voltage is 30kV, syringe needle most advanced and sophisticated with receive spinning 6h under the condition that the cylinder distance is 25cm, 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 70 ℃～90 ℃ 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 2 ℃/min rises to 350 ℃～500 ℃, sintering 2h～6h under 350 ℃～500 ℃ condition then, speed according to 2 ℃/min rises to 700 ℃～1000 ℃ again, sintering 10～14h under 700～1000 ℃ condition promptly gets battery cathode material Re then
2-xA '
xCuO
4 ± δ
Present embodiment is raw materials used all available from Beijing chemical reagents corporation.
Embodiment two: what present embodiment and embodiment one were different is that the polyvinylpyrrolidone ethanolic solution mass concentration described in the step 1 is 9%～13%.Other is identical with embodiment one.
Embodiment three: what present embodiment and embodiment one were different is that the polyvinylpyrrolidone ethanolic solution mass concentration described in the step 1 is 10%.Other is identical with embodiment one.
Embodiment four: what present embodiment and embodiment one, two or three were different is that the Re element described in the step 2 is La, Nd, Sm or Pr.Other is identical with embodiment one, two or three.
Embodiment five: what present embodiment and embodiment four were different is that the A ' element described in the step 2 is Ca, Sr or Ba.Other is identical with embodiment four.
Embodiment six: that present embodiment and embodiment one, two, three or five are different is the Re described in the step 2
2-xA '
xCuO
4 ± δQuality percentage composition in system 1 is 10%～18%.Other is identical with embodiment one, two, three or five.
Embodiment seven: that present embodiment and embodiment one, two, three or five are different is the Re described in the step 2
2-xA '
xCuO
4 ± δQuality percentage composition in system 1 is 15%.Other is identical with embodiment one, two, three or five.
Embodiment eight: present embodiment and embodiment one, two, three or five are different is that the mass ratio of the polyvinylpyrrolidone ethanolic solution that system 1 and step 1 obtain in the step 3 is 3: 1.Other is identical with embodiment one, two, three or five.
Embodiment nine: what present embodiment and embodiment eight were different is that inorganic in the step 5-organic precursor fiber is dried 12h under 80 ℃ condition.Other is identical with embodiment eight.
Embodiment ten: present embodiment and embodiment one, two, three, five, seven or nine are different is sintering 4h, sintering 12h under 900 ℃ condition again under 400 ℃ condition earlier in the step 5.Other is identical with embodiment one, two, three, five, seven or nine.
Embodiment 11: what present embodiment and embodiment one were different is that mixing speed is 35～75 rev/mins in the step 1.Other is identical with embodiment one.
Embodiment 12: what present embodiment and embodiment one were different is that mixing speed is 40～70 rev/mins in the step 1.Other is identical with embodiment one.
Embodiment 13: what present embodiment and embodiment one were different is that mixing speed is 45～65 rev/mins in the step 1.Other is identical with embodiment one.
Embodiment 14: what present embodiment and embodiment one were different is that mixing speed is 50～60 rev/mins in the step 1.Other is identical with embodiment one.
Embodiment 15: what present embodiment and embodiment one were different is that mixing speed is 55 rev/mins in the step 1.Other is identical with embodiment one.
Embodiment 16: what present embodiment and embodiment one were different is that mixing time is 7h in the step 1.Other is identical with embodiment one.
Embodiment 17: what present embodiment and embodiment one were different is that time of repose is 7h～11h in the step 1.Other is identical with embodiment one.
Embodiment 18: what present embodiment and embodiment one were different is that time of repose is 8h～10h in the step 1.Other is identical with embodiment one.
Embodiment 19: what present embodiment and embodiment one were different is that time of repose is 9h in the step 1.Other is identical with embodiment one.
Embodiment 20: the method for electrostatic spinning preparation has K in the present embodiment
2NiF
4The method of the battery cathode material of structure is as follows: one, take by weighing 10g polyvinylpyrrolidone (PVP) powder, join in the conical flask that fills the 114ml ethanolic solution, volatilization for fear of solvent, with stopper with holes bottleneck is sealed, be to stir 6h under 30～80 rev/mins the condition in mechanical agitation speed, at room temperature leave standstill 20h then, obtaining concentration is the polyvinylpyrrolidone ethanolic solution of 10wt%; Two, take by weighing 2.40 gram Nd (NO
3)
3, 0.04 the gram Sr (Ac)
2With 0.60 gram Cu (Ac)
2Be dissolved in 30 ml deionized water, stir and form uniform and transparent mixed solution; Three, the mixed solution that step 2 is obtained joins in the polyvinylpyrrolidone ethanolic solution that step 1 obtains, stir 10h according to 30～80 rev/mins speed again, under the condition of room temperature, leave standstill 10h, obtain the neodymium nitrate/strontium acetate/cupric acetate/PVP colloidal sol of clear; Four, colloidal sol is packed into volume is in the syringe of 20ml, at the syringe pump flow velocity is that 5ml/h, voltage are 30kV, syringe needle tip and are spinning 6h under the condition of 25cm with receiving the cylinder distance, 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 80 ℃ condition, then inorganic-organic precursor fiber is tiled in the alundum (Al porcelain boat, the alundum (Al porcelain boat of Muffle furnace will be placed, speed according to 2 ℃/min rises to 400 ℃, sintering 4h under 400 ℃ condition then, speed according to 2 ℃/min rises to 900 ℃ again, and sintering 12h under 900 ℃ condition promptly gets battery cathode material Nd then
1.93Sr
0.07CuO
4
Present embodiment is raw materials used all available from Beijing chemical reagents corporation.
By Fig. 1 (present embodiment gained battery cathode material Nd
1.93Sr
0.07CuO
4Stereoscan photograph) find out present embodiment gained Nd
1.93Sr
0.07CuO
4Thing is K mutually
2NiF
4Structure, Nd
1.93Sr
0.07CuO
4For fibrous, its diameter is about 200～350nm.
Adopt the complex impedance measuring technology, measure present embodiment gained battery cathode material Nd by making up three-electrode system
1.93Sr
0.07CuO
4With Nd
1.93Sr
0.07CuO
4The cathodic polarization resistance of powder body material, test result such as Fig. 2 (cathodic polarization resistance varies with temperature figure), present embodiment gained battery cathode material Nd
1.93Sr
0.07CuO
4Airborne polarization resistance value (ASR) at 700 ℃ is 0.26Scm
-1, be better than Nd
1.93Sr
0.07CuO
4(the airborne polarization resistance value at 700 ℃ is approximately 0.38Scm to powder body material
-1).
Adopt chronoamperometry to measure present embodiment gained battery cathode material Nd
1.93Sr
0.07CuO
4The work polarization curve.Test atmosphere is air, and probe temperature is 700 ℃.Test result such as Fig. 3 (battery cathode material work polarization curve comparison diagram), the result shows at 58mAcm
-2Current density under present embodiment gained battery cathode material Nd
1.93Sr
0.07CuO
4The cathodic polarization electromotive force be 84mV.And under the same test condition, Sr
0.5Sm
1.5NiO
4The cathodic polarization electromotive force greater than 150mV, at 800 ℃, 20mAcm
-2La under the current density
0.85Sr
0.15MnO
3The cathodic polarization electromotive force be 205mV.This shows present embodiment gained battery cathode material Nd
1.93Sr
0.07CuO
4The performance of electrode is better than Sr
0.5Sm
1.5NiO
4And La
0.85Sr
0.15MnO
3
With present embodiment gained battery cathode material Nd
1.93Sr
0.07CuO
4With Cd
0.1Ce
0.9O
2(made wetting agent in 24 hours according to 1: 1 weight ratio ground and mixed in ball mill with ethanol, abrading-ball is the zirconium oxide microballoons of 1 millimeter of diameter), then mixture is taken out, be the condition lower sheeting of 100Mpa at pressure, 1000 ℃ of following continuous sinterings 24 hours, take out grind into powder once more then.As can be known, sintering is 24 hours under 1000 ℃ of air atmospheres, present embodiment gained battery cathode material Nd by Fig. 4 (the XRD figure spectrum in the present embodiment)
1.93Sr
0.07CuO
4Not with Cd
0.1Ce
0.9O
2Electrolyte generation chemical reaction illustrates present embodiment gained battery cathode material Nd
1.93Sr
0.07CuO
4Chemical stability is good.
Battery cathode material Nd with the present embodiment gained
1.93Sr
0.07CuO
4Grind into powder is then with Nd
1.93Sr
0.07CuO
4Powder and terpinol obtain prepared Chinese ink shape mixture according to the mixed of 1g: 1ml, adopt spin-coating method with 100 rev/mins rotating speed, prepared Chinese ink shape mixture are added drop-wise to the Cd that crosses with 80 orders and 200 order liquid honings in advance
0.1Ce
0.9O
2On potsherd one side surface (every about 0.03 milliliter), make cathode, then it was placed 24 hours in 150 ℃ of baking ovens, then as in the high temperature box furnace, first sintering 8 hours under 500 ℃ of air atmospheres, sintering 4 hours under 1000 ℃ of air atmospheres forms negative electrode/electrolyte assembly then.Platinum slurry (the platinum slurry is already produced by the expensive platinum that grinds) is coated with invests electrolytical opposite side, at 500 ℃ and 850 ℃ sintering 4 hours respectively down, formation anode and reference electrode.Find out that by Fig. 5 (gained cathode surface shape appearance figure) negative electrode has equally distributed crossover network structure.
Battery cathode material Nd with the present embodiment gained
1.93Sr
0.07CuO
4Grind into powder is the condition lower sheeting of 100Mpa at pressure, then 1000 ℃ of following continuous sinterings 24 hours then, take out grind into powder once more, at the 300MPa lower sheeting, again 1000 ℃ of following continuous sinterings 24 hours, obtain potsherd, the potsherd two sides is polished, polishes with 200 order sand paper.
The SETSYS Evolution TMA test macro that adopts French Setaram company to produce is measured the thermal coefficient of expansion of the potsherd after the polishing, and test condition is as follows: work atmosphere is an air, and temperature-measuring range is 100 ℃～900 ℃, and heating rate is 5 ℃/min.Testing result such as Fig. 6: Nd
1.93Sr
0.07CuO
4Thermal coefficient of expansion be 13.5 * 10
-6Cm/cm ℃, Cd
0.1Ce
0.9O
2Thermal coefficient of expansion be 13.1 * 10
-6Cm/cm ℃, and the thermal coefficient of expansion of LSCF (full name) is 15～17 * 10
-6Cm/cm ℃, Nd
1.93Sr
0.07CuO
4Thermal coefficient of expansion near Cd
0.1Ce
0.9O
2, indicating with Nd
1.93Sr
0.07CuO
4Be negative electrode and Cd
0.1Ce
0.9O
2The interface that forms has thermal shock resistance preferably.
Adopt the mixed conductivity of the potsherd after the test of direct current four electrode methods is polished, wherein platinum is done electrode, and test atmosphere is air.Test result such as Fig. 7 (mixed conductivity comparison diagram), the result shows the battery cathode material Nd of present embodiment gained
1.93Sr
0.07CuO
4Mixed conductivity reach 20Scm at 700 ℃
-1When using, require its hybrid conductive rate approaching at 10Scm as the intermediate temperature solid oxide fuel cell cathode material
-1More than, reduce the battery power output consumption that electrode polarization resistance causes, the battery cathode material Nd of present embodiment gained with this
1.93Sr
0.07CuO
4Mixed conductivity change with change of component under the air atmospheres at 750 degree, its conductivity value is at 10-40Scm
-1Between, all reach the requirement of cathode material.
Claims (9)
1. the method for electrostatic spinning preparation has K
2NiF
4The battery cathode material Re of structure
2-xA '
xCuO
4 ± δMethod, it is characterized in that method of electrostatic spinning preparation has K
2NiF
4The battery cathode material Re of structure
2-xA '
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 8%～15% polyvinylpyrrolidone ethanolic solution; Two, according to chemical formula Re
2-xA '
xCuO
4 ± δ, be (2-x): x in the mol ratio of Re element, A ' element, Cu element and O element: 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
2-xA '
xCuO
4 ± δQuality percentage composition in system 1 is 8%～20%, and the Re element is a rare earth element, and A ' element is alkali earth metal Ca, Sr or Ba, chemical formula Re
2-xA '
xCuO
4 ± δIn 0.01＜x＜1,0＜δ＜0.5; Three, the polyvinylpyrrolidone ethanolic solution that system 1 and step 1 are obtained is according to 2～4: 1 mass ratio mixes, stir 10h～12h with 30～80 rev/mins speed, under the condition of room temperature, leave standstill 10h～12h then, obtain colloidal sol: four, with the colloidal sol pinhole aperture of packing into is in the syringe of 0.8mm～1.5mm, at the syringe pump flow velocity is 5ml/h, voltage is 30kV, syringe needle most advanced and sophisticated with receive spinning 6h under the condition that the cylinder distance is 25cm, 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 70 ℃～90 ℃ 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 2 ℃/min rises to 350 ℃～500 ℃, sintering 2h～6h under 350 ℃～500 ℃ condition then, speed according to 2 ℃/min rises to 700 ℃～1000 ℃ again, sintering 10～14h under 700～1000 ℃ condition promptly gets battery cathode material Re then
2-xA '
xCuO
4 ± δ
2. method of electrostatic spinning preparation according to claim 1 has K
2NiF
4The battery cathode material Re of structure
2-xA '
xCuO
4 ± δMethod, it is characterized in that the polyvinylpyrrolidone ethanolic solution mass concentration described in the step 1 is 9%～13%.
3. method of electrostatic spinning preparation according to claim 1 has K
2NiF
4The battery cathode material Re of structure
2-xA '
xCuO
4 ± δMethod, it is characterized in that the polyvinylpyrrolidone ethanolic solution mass concentration described in the step 1 is 10%.
4. has K according to claim 1,2 or 3 described method of electrostatic spinning preparations
2NiF
4The battery cathode material Re of structure
2-xA '
xCuO
4 ± δMethod, it is characterized in that the Re element described in the step 2 is La, Nd, Sm or Pr.
5. has K according to claim 1,2 or 3 described method of electrostatic spinning preparations
2NiF
4The battery cathode material Re of structure
2-xA '
xCuO
4 ± δMethod, it is characterized in that the Re described in the step 2
2-xA '
xCuO
4 ± δQuality percentage composition in system 1 is 10%～18%.
6. has K according to claim 1,2 or 3 described method of electrostatic spinning preparations
2NiF
4The battery cathode material Re of structure
2-xA '
xCuO
4 ± δMethod, it is characterized in that the Re described in the step 2
2-xA '
xCuO
4 ± δQuality percentage composition in system 1 is 15%.
7. has K according to claim 1,2 or 3 described method of electrostatic spinning preparations
2NiF
4The battery cathode material Re of structure
2-xA '
xCuO
4 ± δMethod, it is characterized in that the mass ratio of the polyvinylpyrrolidone ethanolic solution that system in the step 31 and step 1 obtain is 3: 1.
8. method of electrostatic spinning preparation according to claim 7 has K
2NiF
4The battery cathode material Re of structure
2-xA '
xCuO
4 ± δMethod, it is characterized in that inorganic in the step 5-organic precursor fiber dries 12h under 80 ℃ condition.
9. has K according to claim 1,2,3 or 8 described method of electrostatic spinning preparations
2NiF
4The battery cathode material Re of structure
2-xA '
xCuO
4 ± δMethod, it is characterized in that in the step 5 sintering 4h, sintering 12h under 900 ℃ condition again under 400 ℃ condition earlier.
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| CN102054991B (en) * | 2010-11-23 | 2013-01-30 | 北京科技大学 | Cathode material of solid oxide fuel cell and preparation method thereof |
| CN102280646A (en) * | 2011-06-15 | 2011-12-14 | 黑龙江大学 | Method for preparing solid oxide fuel cell cathode material Rel+xA'1-xCuO4+/-Delta with one-dimensional nano-tubular structure by using electrospinning method |
| CN102646836B (en) * | 2012-05-18 | 2015-01-14 | 黑龙江大学 | Preparing method for nano-composite fiber cathode material of solid oxide fuel cell |
| CN103603136A (en) * | 2013-11-11 | 2014-02-26 | 东华大学 | Preparation method of flexible silicon dioxide fiber film |
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