CN105931857A - Preparation method of LaCoO3 sub-micron sphere electrode material with porous structure - Google Patents
Preparation method of LaCoO3 sub-micron sphere electrode material with porous structure Download PDFInfo
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- CN105931857A CN105931857A CN201610410543.XA CN201610410543A CN105931857A CN 105931857 A CN105931857 A CN 105931857A CN 201610410543 A CN201610410543 A CN 201610410543A CN 105931857 A CN105931857 A CN 105931857A
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- 239000007772 electrode material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910002254 LaCoO3 Inorganic materials 0.000 title abstract description 51
- 238000010438 heat treatment Methods 0.000 claims abstract description 91
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000003756 stirring Methods 0.000 claims abstract description 46
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 16
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 16
- 239000000725 suspension Substances 0.000 claims abstract description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- 239000006258 conductive agent Substances 0.000 claims description 15
- 239000006260 foam Substances 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 15
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 14
- 238000000643 oven drying Methods 0.000 claims description 4
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 9
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 5
- 150000004706 metal oxides Chemical class 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000001351 cycling effect Effects 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 abstract 1
- 238000010792 warming Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- 238000012360 testing method Methods 0.000 description 16
- 239000013543 active substance Substances 0.000 description 14
- 238000004140 cleaning Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000003990 capacitor Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 229910000314 transition metal oxide Inorganic materials 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910002445 Co(NO3)3·6H2O Inorganic materials 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002328 LaMnO3 Inorganic materials 0.000 description 1
- 241000877463 Lanio Species 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Hybrid Cells (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
Abstract
This invention relates to a preparation method of LaCoO3 sub-micron sphere electrode material with a porous structure. The method comprises the following steps: dissolving La(NO3).6H2O and Co(NO3)2.6H2O in isopropyl alcohol to form transparent solution; adding glycerol to make the volume ratio of the glycerol and the isopropyl alcohol as 1:4; adding polyvinylpyrrolidone to stir and form homogeneous suspension; filling the suspension into a reaction kettle and reacting at 180 DEG C in an oven; centrifuging the reacted solution and performing centrifugal washing by ethyl alcohol; drying at 70 to 100 DEG C in the oven; putting the obtained reaction product in a tube furnace to perform warming heat treatment in the air so as to obtain the LaCoO3 sub-micron sphere with the porous structure; and making the LaCoO3 sub-micron sphere into the electrode material by a film pushing method. The preparation method provided by the invention firstly compounds the uniform LaCoO3 metal oxide sub-micron sphere with the porous structure through the solvent heating method; the material has the advantages of big specific surface area, good structure stability, good electrical conductivity, long cycling life, and so on.
Description
Technical field
The present invention relates to electrode material for super capacitor and technology of preparing thereof, particularly relate to a kind of novelty for super capacitor
The cobalt acid lanthanum (LaCoO with loose structure of electrode material3) sub-micron ball electrode material preparation method.
Background technology
Along with energy demand is constantly risen and the development of portable electric appts by people, current energy storage equipment is such as
Lithium ion battery, hydrogen fuel cell has been difficult to meet the requirement of people；And cause further as environmental pollution and oil crisis
Day by day exhausted and electric automobile application the extensive prospect inevitable requirement people of fossil energy research and develop energy conversion and the storage of a new generation
Device.Ultracapacitor is owing to having high power density, and the advantage such as excellent cycle life and high current charge-discharge became in recent years
Study hotspot for energy field.
Ultracapacitor is broadly divided into two big classes: a class, based on carbon-based material, is deposited by forming electric double layer in electrode material surface
Storage electric charge, another kind of based on transition metal oxide, carried out by the active substance generation Quick Oxidation reduction reaction on electrode
The storage of electric charge and release.The ultracapacitor wherein prepared with carbon-based material is due to its big specific surface area, different types of hole
Structure is more beneficial for diffusion and the absorption of electrolyte solution intermediate ion, with the ultracapacitor phase prepared with transition metal oxide
Ratio has higher charging and discharging currents density.Electricity is carried out at the adsorption desorption of material surface owing to carbon-based material relies primarily on zwitterion
Lotus storage and release thus during discharge and recharge structural stability the best, super compared to what transition metal oxide was prepared
Level capacitor has more preferable cycle life.But transition metal oxide has higher specific capacity and energy compared with carbon-based material
Metric density. as can be seen here, exploitation has rock-steady structure, and the big novel metal oxide of specific surface area is as electrode of super capacitor material
Material becomes the important directions of ultracapacitor research.
Perovskite type metal oxide is gradually paid close attention to by people as a kind of novel electrode material for super capacitor.2014
J.Tyler Mefford et al. is by LaMnO3Carry out its ultracapacitor electric charge Ultrahigh of Lacking oxygen regulation systematic study.
Yi Cao in 2015 et al. has prepared the LaNiO of Sr doping by method of electrostatic spinning3And LaCoO3And use it for super electricity
Container electrode material.Although calcium titanium oxide has been applied to electrode material for super capacitor, but its preparation process and method
More complicated, the preparation method therefore exploring simple perovskite material is significant in terms of electrode material for super capacitor.
Summary of the invention
In view of the foregoing, the present invention has the LaCoO of loose structure by synthesis3Sub-micron ball electrode material preparation method,
And this material is prepared as electrode of super capacitor.The method is simple, and can prepare in a large number, the LaCoO synthesized3
Loose structure sub-micron ball can reach higher specific capacity for electrode material for super capacitor and cycle performance is excellent.
In order to solve above-mentioned technical problem, the present invention is achieved by the following technical programs:
We have synthesized the LaCoO with loose structure first3Microsphere with submicrometer size is as electrode material, by SEM, TEM
Characterize it can be found that synthesis material have height homogeneity and loose structure, its size probably at about 700-800nm, its
Raw material components and mol ratio are La (NO3)3·6H2O:Co(NO3)2·6H2O=1:1-0.8.
The present invention has the LaCoO of loose structure3Sub-micron ball electrode material preparation method, step is as follows:
(1) by La (NO3)3·6H2O and Co (NO3)2·6H2O is dissolved in isopropanol according to 1:1-0.8 mol ratio and stirs and makes it
Form clear solution；Adding glycerol in solution, making glycerol is 1:4 with the volume ratio of isopropanol, adds polyvinyl pyrrole afterwards
Alkanone stirring becomes homogeneous suspension；Suspension loads reactor 180 DEG C of reactions in an oven；Completely reacted solution from
The heart and use ethanol centrifuge washing, puts into 70～100 DEG C of oven dryings afterwards；
(2) product obtained in step (1) is put in tube furnace intensification heat treatment in air, and heat treatment temperature is
550-650℃；Obtain the LaCoO of loose structure3Sub-micron ball；
(3) by the LaCoO of the loose structure in step (2)3Sub-micron ball is made electrode with catching up with sheet legal system.
Described step (1) polyvinylpyrrolidone addition is preferably (2.5-5) mg/ml.
Described step (1) suspension load reactor in an oven 180 DEG C preferably reaction 6 18 hours.
(1) 70～100 DEG C of oven drying of described step is preferably no less than 12 hours.
Described step (2) intensification heat treatment heating rate be preferably 1-5 DEG C per minute.
Described step (2) heat treatment time is preferably 2-6 hour.
Described step (3) catches up with sheet legal system to be made electrode: the LaCoO of loose structure3Sub-micron ball, conductive agent Super P, viscous
Knot agent PTFE stirs according to mass ratio 8:1:1, rolls into wafer presser on nickel foam collector with catching up with sheet method；By prepare
Working electrode is put in 70 DEG C of baking ovens and is dried no less than 12 hours.
By La (NO3)3·9H2O and Co (NO3)3·6H2O is according to 1:(1-0.8) mol ratio is dissolved in isopropanol and makes its concentration
It is respectively 0.014M:(0.014-0.011) M.
The present invention passes through simple solvent structure LaCoO3 glycerol salt precursor body, and high-temperature heat treatment obtains the most in atmosphere
Having the LaCoO3 sub-micron ball of loose structure, it is homogeneous that this is that first passage solvent thermal process synthesizes pattern, has porous knot
The LaCoO3 metal-oxide sub-micron ball of structure.By three-electrode system, LaCoO3 hollow ball is circulated volt-ampere, constant current
Discharge and recharge and be circulated performance test under the conditions of constant current charge-discharge.It is big that the material synthesized has specific surface area, Stability Analysis of Structures
Property is good, good conductivity, and the advantage such as have extended cycle life.In view of the foregoing, the present invention has the LaCoO3 of loose structure by synthesis
Sub-micron ball electrode material preparation method, and this material is prepared as electrode of super capacitor.The method is simple, and
Can prepare in a large number, the LaCoO3 loose structure sub-micron ball synthesized can reach higher for electrode material for super capacitor
Specific capacity and cycle performance excellent.
Accompanying drawing explanation
Fig. 1 is the LaCoO of the loose structure prepared in embodiment 13Surface sweeping figure after the presoma drying of sub-micron ball.
Fig. 2 is the LaCoO of the loose structure prepared in embodiment 13The scanning figure of sub-micron ball.
Fig. 3 is the LaCoO of the loose structure prepared in embodiment 13The transmission plot of sub-micron ball.
Fig. 4 is the LaCoO of the loose structure prepared in embodiment 13The XRD figure of sub-micron ball.
Fig. 5 is the LaCoO of the loose structure prepared in embodiment 13Sub-micron ball electrode electro Chemical test constant current charge-discharge
Figure.
Fig. 6 is the LaCoO of the loose structure prepared in embodiment 13Sub-micron ball electrode electro Chemical performance test cycle performance
Figure.
Detailed description of the invention
Below by specific embodiment and above-mentioned accompanying drawing, the present invention is described in further detail, below
Embodiment can make those skilled in the art be more completely understood by the present invention, but limits never in any form
The present invention.
Embodiment 1
(1) LaCoO is prepared3Presoma
Weigh 0.4330g La (NO3)3·9H2O、0.2910g Co(NO3)3·6H2O is dissolved in 160ml aqueous isopropanol, adds afterwards
40ml glycerol stirs 5 minutes, then addition 0.75g PVP stirs half an hour in the solution being stirred.The solution being stirred is moved to
200ml water heating kettle is put in baking oven 180 DEG C react 6 hours, after reaction, naturally cool to room temperature.Synthetic presoma is used
Centrifuge separates and uses ethanol eccentric cleaning 3 to 4 times, puts in the baking oven of 70 DEG C and is dried, and drying time is no less than 12 hours.
Dried sample has highly homogeneous porous submicron order spherical structure through SEM test, sees Figure of description 1.
(2) heat treatment LaCoO3Presoma prepares porous LaCoO3 sub-micron ball
The LaCoO that will obtain3Presoma carries out heat treatment in oxygen, and heat treatment temperature is 600 DEG C, and heat treatment time is 1
Hour, 1 DEG C/min of heating rate；Obtain the LaCoO of loose structure3Sub-micron ball；By the sample being thermally treated resulting in is carried out
XRD test proof shows that it is perovskite metal-oxide LaCoO3, see that Figure of description 4. characterizes heat by SEM and TEM
The LaCoO obtained after process3There is homogeneous porous submicron order spherical structure, see Figure of description 2, accompanying drawing 3.
(3) LaCoO is prepared3Working electrode
Active substance is had the LaCoO of loose structure3Sub-micron ball, conductive agent Super P, binding agent PTFE are according to quality
Stir than 8:1:1, roll into wafer presser on nickel foam collector with catching up with sheet method.The working electrode prepared is put into 70 DEG C
Baking oven was dried no less than 12 hours, carries out electrochemical property test with CHI660D work station.By carrying out electrochemistry survey
Examination obtains preferable performance, can be seen that from Figure of description 5 constant current charge-discharge figure and can reach 90F/g under the conditions of 1A/g,
Remain to the specific capacity of 40F/g in high current density 20A/g condition, can be seen that 2A/g from Figure of description 6 cycle performance figure
Under the conditions of circulate 5000 circle still be able to reach the 65% of initial capacity.
Embodiment 2
(1) 0.4330g La (NO is weighed3)3·9H2O、0.2910gCo(NO3)2·6H2O is dissolved in 160ml aqueous isopropanol, it
Rear addition 40ml glycerol stirs 5 minutes, then addition 0.75g PVP stirs half an hour in the solution being stirred.By be stirred
Solution moves to put in 200ml water heating kettle in baking oven 180 DEG C and reacts 6 hours, naturally cools to room temperature after reaction.By synthetic
Presoma separate with centrifuge and use ethanol eccentric cleaning 3 to 4 times, put in the baking oven of 70 DEG C be dried, drying time is many
In 12 hours.
(2) heat treatment LaCoO3Presoma prepares porous LaCoO3 sub-micron ball
The LaCoO that will obtain3Presoma carries out heat treatment in atmosphere, and heat treatment temperature is 600 DEG C, and heat treatment time is 2
Hour, 1 DEG C/min of heating rate, obtain the LaCoO3 sub-micron ball of loose structure；
(3) LaCoO is prepared3Working electrode
Active substance is had the LaCoO of loose structure3Sub-micron ball, conductive agent Super P, binding agent PTFE are according to quality
Stir than 8:1:1, roll into wafer presser on nickel foam collector with catching up with sheet method.The working electrode prepared is put into 70 DEG C of bakings
Case was dried no less than 12 hours, carries out electrochemical property test with CHI660D work station.
Embodiment 3
(1) 0.4330g La (NO is weighed3)3·9H2O、0.2910gCo(NO3)2·6H2O is dissolved in 160ml aqueous isopropanol, it
Rear addition 40ml glycerol stirs 5 minutes, then addition 0.75g PVP stirs half an hour in the solution being stirred.By be stirred
Solution moves to put in 200ml water heating kettle in baking oven 180 DEG C and reacts 6 hours, naturally cools to room temperature after reaction.By synthetic
Presoma separate with centrifuge and use ethanol eccentric cleaning 3 to 4 times, put in the baking oven of 70 DEG C be dried, drying time is many
In 12 hours.
(2) heat treatment LaCoO3Presoma prepares porous LaCoO3 sub-micron ball
The LaCoO that will obtain3Presoma carries out heat treatment in atmosphere, and heat treatment temperature is 600 DEG C, and heat treatment time is 3
Hour, 1 DEG C/min of heating rate, obtain the LaCoO3 sub-micron ball of loose structure；
(3) LaCoO is prepared3Working electrode
Active substance is had the LaCoO of loose structure3Sub-micron ball, conductive agent Super P, binding agent PTFE are according to quality
Stir than 8:1:1, roll into wafer presser on nickel foam collector with catching up with sheet method.The working electrode prepared is put into 70 DEG C of bakings
Case was dried no less than 12 hours, carries out electrochemical property test with CHI660D work station.
Embodiment 4
(1) 0.4330g La (NO is weighed3)3·9H2O、0.2910gCo(NO3)2·6H2O is dissolved in 160ml aqueous isopropanol, it
Rear addition 40ml glycerol stirs 5 minutes, then addition 0.5g PVP stirs half an hour in the solution being stirred.By be stirred
Solution moves to put in 200ml water heating kettle in baking oven 180 DEG C and reacts 6 hours, naturally cools to room temperature after reaction.By synthetic
Presoma separate with centrifuge and use ethanol eccentric cleaning 3 to 4 times, put in the baking oven of 70 DEG C be dried, drying time is many
In 12 hours.
(2) heat treatment LaCoO3Presoma prepares porous LaCoO3 sub-micron ball
The LaCoO that will obtain3Presoma carries out heat treatment in atmosphere, and heat treatment temperature is 600 DEG C, and heat treatment time is 2
Hour, 1 DEG C/min of heating rate, obtain the LaCoO3 sub-micron ball of loose structure；
(3) LaCoO is prepared3Working electrode
Active substance is had the LaCoO of loose structure3Sub-micron ball, conductive agent Super P, binding agent PTFE are according to quality
Stir than 8:1:1, roll into wafer presser on nickel foam collector with catching up with sheet method.The working electrode prepared is put into 70 DEG C of bakings
Case was dried no less than 12 hours, carries out electrochemical property test with CHI660D work station.
Embodiment 5
(1) 0.4330g La (NO is weighed3)3·9H2O、0.2910gCo(NO3)2·6H2O is dissolved in 160ml aqueous isopropanol, it
Rear addition 40ml glycerol stirs 5 minutes, then addition 0.5g PVP stirs half an hour in the solution being stirred.By be stirred
Solution moves to put in 200ml water heating kettle in baking oven 180 DEG C and reacts 6 hours, naturally cools to room temperature after reaction.By synthetic
Presoma separate with centrifuge and use ethanol eccentric cleaning 3 to 4 times, put in the baking oven of 70 DEG C be dried, drying time is many
In 12 hours.
(2) heat treatment LaCoO3Presoma prepares porous LaCoO3 sub-micron ball
The LaCoO that will obtain3Presoma carries out heat treatment in atmosphere, and heat treatment temperature is 600 DEG C, and heat treatment time is 1 little
Time, 1 DEG C/min of heating rate, obtain the LaCoO3 sub-micron ball of loose structure；
(3) LaCoO is prepared3Working electrode
Active substance is had the LaCoO of loose structure3Sub-micron ball, conductive agent Super P, binding agent PTFE are according to quality
Stir than 8:1:1, roll into wafer presser on nickel foam collector with catching up with sheet method.The working electrode prepared is put into 70 DEG C of bakings
Case was dried no less than 12 hours, carries out electrochemical property test with CHI660D work station.
Embodiment 6
(1) 0.4330g La (NO is weighed3)3·9H2O、0.2910gCo(NO3)2·6H2O is dissolved in 160ml aqueous isopropanol, it
Rear addition 40ml glycerol stirs 5 minutes, then addition 0.5g PVP stirs half an hour in the solution being stirred.By be stirred
Solution moves to put in 200ml water heating kettle in baking oven 180 DEG C and reacts 6 hours, naturally cools to room temperature after reaction.By synthetic
Presoma separate with centrifuge and use ethanol eccentric cleaning 3 to 4 times, put in the baking oven of 70 DEG C be dried, drying time is many
In 12 hours.
(2) heat treatment LaCoO3Presoma prepares porous LaCoO3 sub-micron ball
The LaCoO that will obtain3Presoma carries out heat treatment in atmosphere, and heat treatment temperature is 600 DEG C, and heat treatment time is 3 little
Time, 1 DEG C/min of heating rate, obtain the LaCoO3 sub-micron ball of loose structure；
(3) LaCoO is prepared3Working electrode
Active substance is had the LaCoO of loose structure3Sub-micron ball, conductive agent Super P, binding agent PTFE are according to quality
Stir than 8:1:1, roll into wafer presser on nickel foam collector with catching up with sheet method.The working electrode prepared is put into 70 DEG C of bakings
Case was dried no less than 12 hours, carries out electrochemical property test with CHI660D work station.
Embodiment 7
(1) 0.4330g La (NO is weighed3)3·9H2O、0.2910gCo(NO3)2·6H2O is dissolved in 160ml aqueous isopropanol, it
Rear addition 40ml glycerol stirs 5 minutes, then addition 1g PVP stirs half an hour in the solution being stirred.Molten by be stirred
Liquid moves to put in 200ml water heating kettle in baking oven 180 DEG C and reacts 6 hours, naturally cools to room temperature after reaction.By synthetic
Presoma separates with centrifuge and uses ethanol eccentric cleaning 3 to 4 times, puts in the baking oven of 70 DEG C and is dried, and drying time is no less than
12 hours.
(2) heat treatment LaCoO3Presoma prepares porous LaCoO3 sub-micron ball
The LaCoO that will obtain3Presoma carries out heat treatment in atmosphere, and heat treatment temperature is 600 DEG C, and heat treatment time is 2
Hour, 1 DEG C/min of heating rate, obtain the LaCoO3 sub-micron ball of loose structure；
(3) LaCoO is prepared3Working electrode
Active substance is had the LaCoO of loose structure3Sub-micron ball, conductive agent Super P, binding agent PTFE are according to quality
Stir than 8:1:1, roll into wafer presser on nickel foam collector with catching up with sheet method.The working electrode prepared is put into 70 DEG C of bakings
Case was dried no less than 12 hours, carries out electrochemical property test with CHI660D work station.
Embodiment 8
(1) 0.4330g La (NO is weighed3)3·9H2O、0.2910gCo(NO3)2·6H2O is dissolved in 160ml aqueous isopropanol, it
Rear addition 40ml glycerol stirs 5 minutes, then addition 1g PVP stirs half an hour in the solution being stirred.Molten by be stirred
Liquid moves to put in 200ml water heating kettle in baking oven 180 DEG C and reacts 6 hours, naturally cools to room temperature after reaction.By synthetic
Presoma separates with centrifuge and uses ethanol eccentric cleaning 3 to 4 times, puts in the baking oven of 70 DEG C and is dried, and drying time is no less than
12 hours.
(2) heat treatment LaCoO3Presoma prepares porous LaCoO3 sub-micron ball
The LaCoO that will obtain3Presoma carries out heat treatment in atmosphere, and heat treatment temperature is 600 DEG C, and heat treatment time is 1 little
Time, 1 DEG C/min of heating rate, obtain the LaCoO3 sub-micron ball of loose structure；
(3) LaCoO is prepared3Working electrode
Active substance is had the LaCoO of loose structure3Sub-micron ball, conductive agent Super P, binding agent PTFE are according to quality
Stir than 8:1:1, roll into wafer presser on nickel foam collector with catching up with sheet method.The working electrode prepared is put into 70 DEG C of bakings
Case was dried no less than 12 hours, carries out electrochemical property test with CHI660D work station.
Embodiment 9
(1) 0.4330g La (NO is weighed3)3·9H2O、0.2910gCo(NO3)2·6H2O is dissolved in 160ml aqueous isopropanol, it
Rear addition 40ml glycerol stirs 5 minutes, then addition 1g PVP stirs half an hour in the solution being stirred.Molten by be stirred
Liquid moves to put in 200ml water heating kettle in baking oven 180 DEG C and reacts 6 hours, naturally cools to room temperature after reaction.By synthetic
Presoma separates with centrifuge and uses ethanol eccentric cleaning 3 to 4 times, puts in the baking oven of 70 DEG C and is dried, and drying time is no less than
12 hours.
(2) heat treatment LaCoO3Presoma prepares porous LaCoO3 sub-micron ball
The LaCoO that will obtain3Presoma carries out heat treatment in atmosphere, and heat treatment temperature is 600 DEG C, and heat treatment time is 3
Hour, 1 DEG C/min of heating rate, obtain the LaCoO3 sub-micron ball of loose structure；
(3) LaCoO is prepared3Working electrode
Active substance is had the LaCoO of loose structure3Sub-micron ball, conductive agent Super P, binding agent PTFE are according to quality
Stir than 8:1:1, roll into wafer presser on nickel foam collector with catching up with sheet method.The working electrode prepared is put into 70 DEG C
Baking oven was dried no less than 12 hours, carries out electrochemical property test with CHI660D work station.
Embodiment 10
(1) 0.4330g La (NO is weighed3)3·9H2O、0.2910gCo(NO3)2·6H2O is dissolved in 160ml aqueous isopropanol, it
Rear addition 40ml glycerol stirs 5 minutes, then addition 1g PVP stirs half an hour in the solution being stirred.Molten by be stirred
Liquid moves to put in 200ml water heating kettle in baking oven 180 DEG C and reacts 6 hours, naturally cools to room temperature after reaction.By synthetic
Presoma separates with centrifuge and uses ethanol eccentric cleaning 3 to 4 times, puts in the baking oven of 70 DEG C and is dried, and drying time is no less than
12 hours.
(2) heat treatment LaCoO3Presoma prepares porous LaCoO3 sub-micron ball
The LaCoO that will obtain3Presoma carries out heat treatment in atmosphere, and heat treatment temperature is 550 DEG C, and heat treatment time is 2
Hour, 1 DEG C/min of heating rate, obtain the LaCoO3 sub-micron ball of loose structure；
(3) LaCoO is prepared3Working electrode
Active substance is had the LaCoO of loose structure3Sub-micron ball, conductive agent Super P, binding agent PTFE are according to quality
Stir than 8:1:1, roll into wafer presser on nickel foam collector with catching up with sheet method.The working electrode prepared is put into 70 DEG C
Baking oven was dried no less than 12 hours, carries out electrochemical property test with CHI660D work station.
Embodiment 11
(1) 0.4330g La (NO is weighed3)3·9H2O、0.2910gCo(NO3)2·6H2O is dissolved in 160ml aqueous isopropanol, it
Rear addition 40ml glycerol stirs 5 minutes, then addition 1g PVP stirs half an hour in the solution being stirred.Molten by be stirred
Liquid moves to put in 200ml water heating kettle in baking oven 180 DEG C and reacts 6 hours, naturally cools to room temperature after reaction.By synthetic
Presoma separates with centrifuge and uses ethanol eccentric cleaning 3 to 4 times, puts in the baking oven of 70 DEG C and is dried, and drying time is no less than
12 hours.
(2) heat treatment LaCoO3Presoma prepares porous LaCoO3 sub-micron ball
The LaCoO that will obtain3Presoma carries out heat treatment in atmosphere, and heat treatment temperature is 650 DEG C, and heat treatment time is 2
Hour, 1 DEG C/min of heating rate, obtain the LaCoO3 sub-micron ball of loose structure；
(3) LaCoO is prepared3Working electrode
Active substance is had the LaCoO of loose structure3Sub-micron ball, conductive agent Super P, binding agent PTFE are according to quality
Stir than 8:1:1, roll into wafer presser on nickel foam collector with catching up with sheet method.The working electrode prepared is put into 70 DEG C
Baking oven was dried no less than 12 hours, carries out electrochemical property test with CHI660D work station.
Embodiment 12
(1) 0.4330g La (NO is weighed3)3·9H2O、0.2328gCo(NO3)2·6H2O is dissolved in 160ml aqueous isopropanol, it
Rear addition 40ml glycerol stirs 5 minutes, then addition 0.5g PVP stirs half an hour in the solution being stirred.By be stirred
Solution moves to put in 200ml water heating kettle in baking oven 180 DEG C and reacts 6 hours, naturally cools to room temperature after reaction.By synthetic
Presoma separate with centrifuge and use ethanol eccentric cleaning 3 to 4 times, put in the baking oven of 70 DEG C be dried, drying time is many
In 12 hours.
(2) heat treatment LaCoO3Presoma prepares porous LaCoO3 sub-micron ball
The LaCoO that will obtain3Presoma carries out heat treatment in atmosphere, and heat treatment temperature is 600 DEG C, and heat treatment time is 2
Hour, 3 DEG C/min of heating rate, obtain the LaCoO3 sub-micron ball of loose structure；
(3) LaCoO is prepared3Working electrode
Active substance is had the LaCoO of loose structure3Sub-micron ball, conductive agent Super P, binding agent PTFE are according to quality
Stir than 8:1:1, roll into wafer presser on nickel foam collector with catching up with sheet method.The working electrode prepared is put into 70 DEG C
Baking oven was dried no less than 12 hours, carries out electrochemical property test with CHI660D work station.
Embodiment 13
(1) 0.4330g La (NO is weighed3)3·9H2O、0.2619gCo(NO3)2·6H2O is dissolved in 160ml aqueous isopropanol, it
Rear addition 40ml glycerol stirs 5 minutes, then addition 0.5g PVP stirs half an hour in the solution being stirred.By be stirred
Solution moves to put in 200ml water heating kettle in baking oven 180 DEG C and reacts 6 hours, naturally cools to room temperature after reaction.By synthetic
Presoma separate with centrifuge and use ethanol eccentric cleaning 3 to 4 times, put in the baking oven of 70 DEG C be dried, drying time is many
In 12 hours.
(2) heat treatment LaCoO3Presoma prepares porous LaCoO3 sub-micron ball
The LaCoO that will obtain3Presoma carries out heat treatment in atmosphere, and heat treatment temperature is 600 DEG C, and heat treatment time is 2
Hour, 5 DEG C/min of heating rate, obtain the LaCoO3 sub-micron ball of loose structure；
(3) LaCoO is prepared3Working electrode
Active substance is had the LaCoO of loose structure3Sub-micron ball, conductive agent Super P, binding agent PTFE are according to quality
Stir than 8:1:1, roll into wafer presser on nickel foam collector with catching up with sheet method.The working electrode prepared is put into 70 DEG C
Baking oven was dried no less than 12 hours, carries out electrochemical property test with CHI660D work station.
Every key parameter and the chemical property testing result of the embodiment of the present invention see table.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention being not restricted to the described embodiments,
Embodiment of above is only used for explaining claims.So protection scope of the present invention is not limited to description.Any it is familiar with basis
Those skilled in the art in the technical scope of present disclosure, the change that can readily occur in or replacement, be included in this
Within the protection domain of invention.
Claims (7)
1. there is the LaCoO of loose structure3Sub-micron ball electrode material preparation method, is characterized in that step is as follows:
(1) by La (NO3)3·6H2O and Co (NO3)2·6H2O is dissolved in isopropanol according to 1:1-0.8 mol ratio and stirs and makes it
Form clear solution；Adding glycerol in solution, making glycerol is 1:4 with the volume ratio of isopropanol, adds polyvinylpyrrolidine afterwards
Ketone stirring becomes homogeneous suspension；Suspension loads reactor 180 DEG C of reactions in an oven；Completely reacted solution centrifugal
And use ethanol centrifuge washing, put into 70～100 DEG C of oven dryings afterwards；
(2) product obtained in step (1) is put in tube furnace intensification heat treatment in air, and heat treatment temperature is 550-650
℃；Obtain the LaCoO of loose structure3Sub-micron ball；
(3) by the LaCoO of the loose structure in step (2)3Sub-micron ball is made electrode with catching up with sheet legal system.
2. the method for claim 1, is characterized in that polyvinylpyrrolidone addition is for (2.5-5) mg/ml.
3. the method for claim 1, it is characterized in that suspension load reactor in an oven 180 DEG C react 6 18 hours.
4. the method for claim 1, is characterized in that 70～100 DEG C of oven dryings were no less than 12 hours.
5. the method for claim 1, it is characterized in that step (2) intensification heat treatment heating rate be 1-5 DEG C per minute.
6. the method for claim 1, is characterized in that step (2) heat treatment time is 1-3 hour.
7. the method for claim 1, is characterized in that step (3) is caught up with sheet legal system to be made electrode and is: the LaCoO of loose structure3
Sub-micron ball, conductive agent Super P, binding agent PTFE stir according to mass ratio 8:1:1, roll into wafer presser with catching up with sheet method
On nickel foam collector；The working electrode prepared is put in 70 DEG C of baking ovens and be dried no less than 12 hours.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106783200A (en) * | 2016-11-30 | 2017-05-31 | 天津大学 | A kind of preparation method of the copper cobalt sulphur microballoon electrode material with hollow structure |
| CN110449160A (en) * | 2019-07-30 | 2019-11-15 | 天津大学 | Cation doping acid lanthanum material and preparation method thereof for electro-catalysis purification of organic waste water |
| CN110517894A (en) * | 2019-08-29 | 2019-11-29 | 武汉理工大学 | Based on cobalt acid lanthanum, the asymmetric capacitor of graphene oxide and preparation method thereof |
| US20200262760A1 (en) * | 2017-09-22 | 2020-08-20 | Sumitomo Chemical Company, Limited | Composition, Film, and Method for Producing Film |
| CN112045812A (en) * | 2020-07-27 | 2020-12-08 | 安徽阜南县万家和工艺品有限公司 | Treatment process for improving cool contact feeling of wicker deck chair |
| CN112266026A (en) * | 2020-10-30 | 2021-01-26 | 常州大学 | Method for preparing cobaltate perovskite material |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101172661A (en) * | 2007-08-08 | 2008-05-07 | 中北大学 | Method of producing ultra-fine perovskite type LaFeO*, LaMnO*, LaNiO* |
| CN101428223A (en) * | 2008-12-05 | 2009-05-13 | 厦门大学 | Photocatalyst and its preparing process |
| CN102784650A (en) * | 2012-08-07 | 2012-11-21 | 上海师范大学 | Hollow La2NiO4 microsphere catalyst and preparation method thereof |
| CN103021678A (en) * | 2013-01-22 | 2013-04-03 | 电子科技大学 | Preparation of super capacitor film electrode capable of charging and discharging at ultra-high rate |
-
2016
- 2016-06-08 CN CN201610410543.XA patent/CN105931857B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101172661A (en) * | 2007-08-08 | 2008-05-07 | 中北大学 | Method of producing ultra-fine perovskite type LaFeO*, LaMnO*, LaNiO* |
| CN101428223A (en) * | 2008-12-05 | 2009-05-13 | 厦门大学 | Photocatalyst and its preparing process |
| CN102784650A (en) * | 2012-08-07 | 2012-11-21 | 上海师范大学 | Hollow La2NiO4 microsphere catalyst and preparation method thereof |
| CN103021678A (en) * | 2013-01-22 | 2013-04-03 | 电子科技大学 | Preparation of super capacitor film electrode capable of charging and discharging at ultra-high rate |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106783200A (en) * | 2016-11-30 | 2017-05-31 | 天津大学 | A kind of preparation method of the copper cobalt sulphur microballoon electrode material with hollow structure |
| CN106783200B (en) * | 2016-11-30 | 2018-12-18 | 天津大学 | A kind of preparation method of the copper cobalt sulphur microballoon electrode material with hollow structure |
| US20200262760A1 (en) * | 2017-09-22 | 2020-08-20 | Sumitomo Chemical Company, Limited | Composition, Film, and Method for Producing Film |
| US11958783B2 (en) * | 2017-09-22 | 2024-04-16 | Sumitomo Chemical Company, Limited | Composition, film, and method for producing film |
| CN110449160A (en) * | 2019-07-30 | 2019-11-15 | 天津大学 | Cation doping acid lanthanum material and preparation method thereof for electro-catalysis purification of organic waste water |
| CN110517894A (en) * | 2019-08-29 | 2019-11-29 | 武汉理工大学 | Based on cobalt acid lanthanum, the asymmetric capacitor of graphene oxide and preparation method thereof |
| CN112045812A (en) * | 2020-07-27 | 2020-12-08 | 安徽阜南县万家和工艺品有限公司 | Treatment process for improving cool contact feeling of wicker deck chair |
| CN112266026A (en) * | 2020-10-30 | 2021-01-26 | 常州大学 | Method for preparing cobaltate perovskite material |
| CN112266026B (en) * | 2020-10-30 | 2024-01-26 | 常州大学 | Method for preparing cobaltate perovskite material |
| CN116060050A (en) * | 2023-01-03 | 2023-05-05 | 陕西科技大学 | Self-assembled lanthanum cobaltate microsphere/silver phosphate nano-composite light-responsive antibacterial agent, and preparation method and application thereof |
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