CN104538206B - Application of the one perovskite-like oxide in ultracapacitor - Google Patents
Application of the one perovskite-like oxide in ultracapacitor Download PDFInfo
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- CN104538206B CN104538206B CN201410768744.8A CN201410768744A CN104538206B CN 104538206 B CN104538206 B CN 104538206B CN 201410768744 A CN201410768744 A CN 201410768744A CN 104538206 B CN104538206 B CN 104538206B
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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
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- Y02E60/13—Energy storage using capacitors
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Abstract
The invention belongs to ultracapacitor field, and in particular to application of the perovskite-like oxide in ultracapacitor.The structural formula of perovskite oxide is AB1‑yMyO3‑δ；The one kind or mixing of wherein A cation for Sr or Ba alkaline-earth metal ions；B cations are Co；M is the one or more in Ti, Nb, Fe, Sn, Cr or Mo；0.05≤y≤0.2,0≤δ≤1.Perovskite oxide of the present invention, preparation method is simple to operate, it is not necessary to complex device, and whole preparation process is affected by environment small, it is adaptable to mass produce.The present invention widened the scope of electrode of super capacitor active material there is provided electrode material, be a kind of excellent super capacitor material while having higher electrochemical stability not only with higher specific capacitance.
Description
Technical field
The present invention relates to application of the perovskite-like oxide in ultracapacitor, belong to ultracapacitor field.
Background technology
The energy is the important foundation that human survival and society well develop, with the progress of science and technology, electric automobile, boat
Empty space flight, mobile communication, science and techniques of defence, generation of electricity by new energy (wind energy, solar energy etc.) and the development of electromagnet weapon, people couple
The demand of high-performance storage device power supply is more and more urgent.These energy storage devices are right in addition to it there are certain requirements to energy density
The requirement of power density also more and more higher.Super capacitor is as a kind of novel energy-storing element in this context, because its power is close
Degree is high, have extended cycle life, charging rate is fast, wide temperature in use scope, safety and environmental protection the advantages of, receive more and more attention,
Important component as new energy application field.
Carbon material is smaller due to its specific capacitance, and preparation technology is complicated, limits it and further develops；Metal oxide by
In with high specific capacitance and excellent cyclic reversibility, therefore it is considered as optimal electrode material.In metal oxide
In electrode material, ruthenium-oxide with very high specific capacitance due to, by universal concern, but its high cost, low hole, having
Malicious the shortcomings of, limits its large-scale practical application.
Current perovskite material is applied to ultracapacitor field and there is a small amount of research, is related to the specific capacitance and carbon materials of material
Material is close.Such as LaFeO3-δSpecific capacitance value be about 200F/g, La0.7Al0.3FeO3-δSpecific capacitance value be about 260F/g,
SrCoO2.5Specific capacitance value be about 170F/g (F.Xiao et al.Materials Chemistry and Physics,
2005,94221–225；A.Rai et al.Solid State Ionics,2014,262,230–233.).
Consequently found that new perovskite material is used for ultracapacitor, it is set to be provided simultaneously with bigger specific capacitance and simple
Preparation technology, low cost, the advantages of nontoxic, for promoting the large-scale practical application of ultracapacitor to be significant.
The content of the invention
The invention aims to the perovskite electrode material for super capacitor and carbon material for solving presently, there are, than electricity
Hold smaller；The problem of metal oxide electrode material preparation technology is complicated, and the class provided has bigger specific capacitance and letter
Application of the perovskite oxide of single preparation technology in ultracapacitor.
The technical scheme is that：Application of the one perovskite-like oxide in ultracapacitor, it is characterised in that：Calcium
The structural formula of titanium ore oxide is AB1-yMyO3-δ；The one kind or mixing of wherein A cation for Sr or Ba alkaline-earth metal ions；B
Position cation is Co；M is one kind or several in (oxidation state is more than or equal to the transition metal of trivalent) Ti, Nb, Fe, Sn, Cr or Mo
Kind；0.05≤y≤0.2,0≤δ≤1.
Structural formula is AB1-yMyO3-δPerovskite material be preferably Ba0.5Sr0.5Co0.8Fe0.2O3-δ、SrCo0.9Nb0.1O3-δ
Or SrCo0.9Ti0.1O3-δ。
Structure above is AB1-yMyO3-δPerovskite oxide be as electrode active material be applied to super capacitor
Device.
Structure above is AB1-yMyO3-δPerovskite oxide preparation method be using simple solid phase method or
EDTA-CA collosol and gels joint complexometry (W.Zhou et al.International Journal of Hydrogen
Energy,2010,35,1356–1366；PY Zeng et al.Journal of Membrane Science,2007,302,
171–9.).Ultracapacitor is applied to as electrode material, not only with higher specific capacitance, higher electrochemical stability,
Preparation technology is simple simultaneously.
The test of perovskite oxide chemical property：
The preparation of working electrode：Perovskite oxide powder, Super P, PTFE binding agent in mass ratio 80:15:5 with fitting
Measure absolute ethyl alcohol and into pasty state, after being dried in 60 DEG C of baking ovens, be pressed into area about 1cm2Disk.In 100 DEG C of vacuum drying chambers
Dry after 12h, be clipped in two panels circular shaped foam nickel, in immersion electrolyte.
Constant current charge-discharge test and cyclical stability test are carried out using Shenzhen Neware 5V-50mA cell testers.
First, the electrolytic cell for filling electrolyte is fixed on reference electrode, platinum plate electrode with the working electrode of perovskite oxide type
In, constitute three-electrode system.Then the voltage range with constant electric current to research system in setting carries out charge/discharge survey
Examination.
Cyclic voltammetry is carried out using the electrochemical workstations of Princeton Princeton 2273.First, perovskite is used
The working electrode of type oxide type is fixed in the electrolytic cell for filling electrolyte with reference electrode, platinum plate electrode, constitutes three electrodes
System.By controlling constant sweep speed from take-off potential V1Change to current potential V2, then again with same speed from current potential V2
Change to V1, or in current potential V1With current potential V2Between repeatedly scan round, response current can be produced in scanning process.
Beneficial effect：
The perovskite oxide material being related to, combines complexometry, work using traditional solid phase method or EDTA-CA collosol and gels
Skill, preparation method are simple, it is not necessary to complex device, and whole preparation process is affected by environment small, it is adaptable to mass produce.As
During electrode material for super capacitor, the carbon-based material commonly used more at present and the perovskite material studied, with bigger ratio
Electric capacity, such as SrCo0.9Nb0.1O3-δThe specific capacitance value of powder reaches 405F/g, and these beneficial effects will be greatly facilitated ultracapacitor
Large-scale practical application.
Brief description of the drawings
Fig. 1 is the X-ray diffraction curve of perovskite powder prepared by Example 1 and Example 2 of the present invention；Wherein a is real
Apply the SrCo of the preparation of example 10.9Nb0.1O3-δThe X-ray diffraction curve map of powder；B is SrCo prepared by embodiment 20.9Ti0.1O3-δPowder
The X-ray diffraction curve map of body；
Fig. 2 is SrCo prepared by the embodiment of the present invention 10.9Nb0.1O3-δCyclic voltammetric (CV) under different scanning rates is bent
Line；Wherein (a) is 5mv/s, and (b) is 10mv/s, and (c) is 20mv/s, and (d) is 50mv/s；
Fig. 3 is SrCo prepared by the embodiment of the present invention 20.9Ti0.1O3-δCyclic voltammetric (CV) under different scanning rates is bent
Line；Wherein (a) is 5mv/s, and (b) is 10mv/s, and (c) is 20mv/s, and (d) is 50mv/s；
Fig. 4 is SrCo prepared by the embodiment of the present invention 10.9Nb0.1O3-δConstant current charge-discharge curve under different current densities；
Wherein (a) is 0.5A/g, and (b) is 10A/g, and (c) is 2A/g, and (d) is 5A/g；(e)10A/g；
Fig. 5 is SrCo prepared by the embodiment of the present invention 20.9Ti0.1O3-δConstant current charge-discharge curve under different current densities；
Wherein (a) is 0.5A/g, and (b) is 10A/g, and (c) is 2A/g, and (d) is 5A/g；(e)10A/g；
Fig. 6 is 1SrCo of the embodiment of the present invention0.9Nb0.1O3-δCycle performance curve；
Fig. 7 is 2SrCo of the embodiment of the present invention0.9Ti0.1O3-δCycle performance curve；
Fig. 8 is 3Ba of the embodiment of the present invention0.5Sr0.5Co0.8Fe0.2O3-δCycle performance curve.
Embodiment
Material involved in the present invention includes but is not limited to the material in following examples, involved preparation method
Comprising but be not limited to the preparation method in following examples.
Embodiment 1:SrCo0.9Nb0.1O3-δPerovskite oxide material
SrCo0.9Nb0.1O3-δThe method that the preparation of powder is used is conventional solid-state method.First, stoichiometrically distinguish
Weigh SrCO3、Co3O4、Nb2O5Powder is put into high energy ball milling tank, and is put into high-energy ball milling instrument (FRITSCH, Pulverisette
6) ball milling 120min in, until well mixed.Then, slurry is taken out and is placed on below sodium vapor lamp and dried.Finally, it will obtain
Powder is put into high temperature furnace, and is calcined 20h under 1200 DEG C of air atmosphere, obtains into the SrCo of phase0.9Nb0.1O3-δPowder, such as
Shown in Fig. 1 a.Prepared SrCo0.9Nb0.1O3-δCyclic voltammetric (CV) curve under different scanning rates is as shown in Figure 2；Prepare
SrCo0.9Nb0.1O3-δConstant current charge-discharge curve under different current densities is as shown in Figure 4.
By perovskite oxide chemical property test the step of test, the material compares under 0.5A/g current density
Capacity cycle performance for 405F/g and more stably, as shown in Figure 6.
Embodiment 2:SrCo0.9Ti0.1O3-δPerovskite oxide material
SrCo0.9Ti0.1O3-δThe method that the preparation of powder is used is EDTA-CA collosol and gels joint complexometry.First,
Sr (NO are stoichiometrically weighed respectively3)2、Co(NO3)2Particle, solution of tetrabutyl titanate are put into beaker, agitating and heating, etc.
After all being dissolved to all particles, by metal ion：EDTA：CA mol ratio is 1:1:1.5, add two kinds of complexings of EDTA, CA
Agent.Add NH3·H2O adjusts the pH value of solution to 6 or so.Secondly, beaker is placed on warm table be heated with stirring to always it is molten
Glue, and be put into 250 DEG C of baking oven and be calcined 4h, obtain SrCo0.9Ti0.1O3-δPresoma.Finally, by SrCo0.9Ti0.1O3-δ
Presoma be put into high temperature furnace, be calcined 10h under 1100 DEG C of air atmosphere, obtain into the SrCo of phase0.9Ti0.1O3-δPowder
Body, as shown in Figure 1 b.The SrCo of preparation0.9Ti0.1O3-δCyclic voltammetric (CV) curve under different scanning rates is as shown in Figure 3；System
Standby SrCo0.9Ti0.1O3-δConstant current charge-discharge curve under different current densities is as shown in Figure 5.
Tested by foregoing testing procedure, material specific capacity under 0.5A/g current density is 375F/g and more stably
Cycle performance, as shown in Figure 7.
Embodiment 3:Ba0.5Sr0.5Co0.8Fe0.2O3-δPerovskite oxide material
Ba0.5Sr0.5Co0.8Fe0.2O3-δThe method that the preparation of powder is used is that the EDTA-CA colloidal sols described in embodiment 2 coagulate
Glue combines complexometry.First, Ba (NO are stoichiometrically weighed respectively3)2、Sr(NO3)2、Co(NO3)2、Fe(NO3)3Particle, is stirred
Heating is mixed, after all particles all dissolve, by metal ion：EDTA：CA mol ratio is 1:1:1.5, add EDTA, CA
Two kinds of complexing agents.Add NH3·H2O adjusts the pH value of solution to 6 or so.Secondly, beaker is placed on warm table and stirred always
Colloidal sol shape is heated to, and is put into 250 DEG C of baking oven and is calcined 4h, Ba is obtained0.5Sr0.5Co0.8Fe0.2O3-δPresoma.Finally,
By Ba0.5Sr0.5Co0.8Fe0.2O3-δPresoma be put into high temperature furnace, be calcined 5h under 850 DEG C of air atmosphere, obtain into
The Ba of phase0.5Sr0.5Co0.8Fe0.2O3-δPowder.
Tested by foregoing testing procedure, material specific capacity under 1A/g current density is 357F/g and more stably followed
Ring performance, as shown in Figure 8.
Claims (1)
1. application of the perovskite-like oxide in ultracapacitor, it is characterised in that：The structural formula of perovskite oxide is
SrCo0.9Nb0.1O3-δ；The specific capacitance value of described perovskite oxide is 405F/g.
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| CN105632788B (en) * | 2016-02-29 | 2017-09-19 | 东南大学 | Active material BaCoF4Super capacitor of working electrode and preparation method thereof |
| CN108987125B (en) * | 2018-08-13 | 2021-04-16 | 云南大学 | Perovskite stannate supercapacitor electrode material, preparation method and application |
| CN113658808B (en) * | 2021-07-21 | 2023-02-03 | 太原理工大学 | Magnesium-doped perovskite structure high-entropy ceramic electrode material and application thereof in preparation of supercapacitor |
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| CN1732540A (en) * | 2002-12-27 | 2006-02-08 | Tdk株式会社 | Thin film capacitor and method for fabricating the same |
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| CN101252190B (en) * | 2008-04-01 | 2010-10-13 | 南京工业大学 | Mixing electric conduction type middle-low temperature fuel cell cathode material and preparing method thereof |
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| CN1732540A (en) * | 2002-12-27 | 2006-02-08 | Tdk株式会社 | Thin film capacitor and method for fabricating the same |
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| ıhollow fibre membranes.《Separation and Purification Technology》.2011,第78卷第175-180页. * |
| Bo Meng等.Preparation and oxygen permeation properties of SrCo0.9Nb0.1O3− * |
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| Structural, electrical and electrochemical characterizations of SrNb0.1Co0.9O3Ld as a cathode of solid oxide fuel cells operating below 600℃;Wei Zhou等;《International journal of hydrogen energy》;20091222;第35卷;第1356-1366页 * |
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