CN110277252A - A kind of supercapacitor tin-antiomony oxide/holimium oxide/tin indium oxide combination electrode material and preparation method thereof - Google Patents
A kind of supercapacitor tin-antiomony oxide/holimium oxide/tin indium oxide combination electrode material and preparation method thereof Download PDFInfo
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- CN110277252A CN110277252A CN201910592329.4A CN201910592329A CN110277252A CN 110277252 A CN110277252 A CN 110277252A CN 201910592329 A CN201910592329 A CN 201910592329A CN 110277252 A CN110277252 A CN 110277252A
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- 239000007772 electrode material Substances 0.000 title claims abstract description 68
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 238000002604 ultrasonography Methods 0.000 claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 9
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000002525 ultrasonication Methods 0.000 claims abstract description 5
- 239000006185 dispersion Substances 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 23
- 239000006260 foam Substances 0.000 claims description 17
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- 238000004140 cleaning Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- XXLJGBGJDROPKW-UHFFFAOYSA-N antimony;oxotin Chemical compound [Sb].[Sn]=O XXLJGBGJDROPKW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 abstract description 17
- 239000000126 substance Substances 0.000 abstract 1
- 229910001887 tin oxide Inorganic materials 0.000 abstract 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 25
- 239000002033 PVDF binder Substances 0.000 description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 12
- 238000012545 processing Methods 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 230000005611 electricity Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 229910052689 Holmium Inorganic materials 0.000 description 2
- CHBCHAGCVIMDKI-UHFFFAOYSA-N [F].C=C Chemical group [F].C=C CHBCHAGCVIMDKI-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002834 transmittance Methods 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
- H01G11/84—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)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of supercapacitor tin-antiomony oxide/holimium oxide/indium-tin oxide electrode materials and preparation method thereof.The preparation method comprises the following steps: 1) impregnating substrate in dilute hydrochloric acid, then clean repeatedly；Then substrate constant temperature is dried；2) tin-antiomony oxide, holimium oxide and Kynoar are mixed and is dissolved in solvent, obtain solution A；Tin indium oxide, holimium oxide and Kynoar are mixed and are dissolved in solvent, solution B is obtained；By solution A and the removing dispersion of B ultrasound sound under ultrasonication；3) taking solution A, note is added in substrate by several times, and note is dry after adding, and then taking solution B, note is added on the primary electrode material by several times, is then dried, is obtained the combination electrode material.The combination electrode material has excellent chemical property, and capacitor still is able to retain original 79% or more after 10000 circle of circulation, and coulombic efficiency is still close to 98% or more.
Description
Technical field
The invention belongs to supercapacitor technologies fields, and in particular to a kind of supercapacitor with tin-antiomony oxide/holimium oxide/
Tin indium oxide combination electrode material and preparation method thereof.
Technical background
Supercapacitor as a kind of novel energy storage device, have green, environmental protection, the charging time is short, power density is big,
The advantages that good cycle, long service life, become research hotspot over nearly more than 20 years, people are also constantly exploring capacitor and electricity
" superbattery " of pond mixture.Supercapacitor is divided into electric double layer capacitance, fake capacitance and hybrid electricity by stored energy form difference
Hold, compared with battery, although supercapacitor power density is larger, energy density influences its performance lower than batteries such as silicon, lithiums
Factor mainly have electrode material, electrolyte and diaphragm etc., wherein limit its performance primary factor be electrode material.Super electricity
Container electrode material mainly includes transition metal oxide, conducting polymer, nitride, sulfide, MOF, COF and carbon material
Deng in recent years, improving the research of material capacitive property repeatly using the recombination of homogeneous electrode material or inhomogeneity electrode material combinations
See not fresh, while the new electrode materials of non-combined type also gradually occur with the progress of different sciemtifec and technical spheres, therefore, using recombination
The electrode material of current material synthesized high-performance develops novel electrode material as research hotspot and difficult point instantly.
Important electrode material of the metal oxide as supercapacitor utilizes on electrode surface two-dimensional space quickly
The absorption of the undercurrent potential of Faraday effect and ion and desorption carry out energy stores and output, up to very high specific capacitance.Although
Transition metal oxide electrode material can reach higher specific capacitance, but its electric conductivity is poor, follows mostly for existing metal oxide
Ring performance is unstable, operating voltage is lower, to limit its further applying in supercapacitor.
Summary of the invention
By in consideration of it, the present invention provides a kind of supercapacitor tin-antiomony oxide/holimium oxide/oxygen to overcome above-mentioned deficiency
Change indium tin combination electrode material and preparation method thereof, by being formed after disperse system using tin-antiomony oxide and holimium oxide first in substrate
Upper attachment prepares tin-antiomony oxide/holimium oxide primary electrode material, then by the way that tin indium oxide/holimium oxide is dispersed in tin oxide
Antimony primary electrode material can be obtained tin-antiomony oxide/holimium oxide/tin indium oxide combination electrode material.
The purpose of the present invention is realized at least through one of following technical solution.
A kind of supercapacitor tin-antiomony oxide/holimium oxide/tin indium oxide combination electrode material preparation method, including with
Lower step:
(1) base material pre-processes
Firstly, substrate is impregnated in dilute hydrochloric acid, then cleaned repeatedly with deionized water；Then the substrate after cleaning is subjected to constant temperature
It is dried；
(2) tin-antiomony oxide/holimium oxide and tin indium oxide/holimium oxide solution are prepared
Tin-antiomony oxide, holimium oxide and Kynoar are mixed and are dissolved in solvent, solution A is obtained；By solution A under ultrasonication
Ultrasound removing dispersion；Tin indium oxide, holimium oxide and Kynoar are mixed and are dissolved in solvent, solution B is obtained；In ultrasonication
Lower remove solution B ultrasound is dispersed；
(3) tin-antiomony oxide/holimium oxide/tin indium oxide combination electrode material is prepared
Base material by step (1) processing is fixed in heating environment, and taking solution A, note is added on step (1) processing by several times
In substrate afterwards, it is dried after the completion of infusing and adding, obtains tin-antiomony oxide/holimium oxide primary electrode material；Solution B is taken to infuse by several times
It is added on tin-antiomony oxide/holimium oxide primary electrode material, is dried after the completion of infusing and adding, obtains the tin-antiomony oxide/oxidation
Holmium/tin indium oxide combination electrode material.
It is highly preferred that it is characterized by: the substrate is nickel foam or foam copper in the step (1).
It is highly preferred that drying temperature is 40-60 DEG C it is characterized by: soaking time is 10-60s in the step (1),
Drying time is 2-6 h.
It is highly preferred that tin-antiomony oxide, holimium oxide and the Kynoar mass ratio in the step (2) in solution A are 6-
8:1-3:1, tin indium oxide, holimium oxide and Kynoar mass ratio are 6-8:1-3:1 in solution B.Tin-antiomony oxide and holimium oxide
Mass concentration in solution A is 10-25mg/mL, and the mass concentration of tin indium oxide and holimium oxide in solution B is 10-25mg/
mL。
It is highly preferred that the ultrasonic splitting time of solution A and solution B is 7-12h in the step (2), temperature when ultrasonic
Degree is 25-35 DEG C.
It is furthermore preferred that the time interval that gradation note adds in the step (3) is 3-10min, drying time after the completion of note adds
For 4-12h, drying temperature is 50-80 DEG C.
It is furthermore preferred that in the step (2), solvent is NMP in solution A and B.
It is furthermore preferred that the volume ratio of note adds in step (4) solution A and solution B is 1:1-7:1.
Supercapacitor tin-antiomony oxide/holimium oxide/tin indium oxide combination electrode the material that above-mentioned preparation method obtains
Material.
The present invention selects tin indium oxide and tin-antiomony oxide as composite oxides, is based on the good conduction of such oxide
Performance and both containing the similitude of element, this not only contributes to the conduction of charge, is also beneficial to electrolyte ion and electricity
Common element collaboration transmitting effect in lotus transmittance process.Since holimium oxide has very strong magnetism, stronger magnetic can be generated
, small amounts holmium is added while two oxides is compound, the perturbation action of ion and charge will be increased, so that electrode is steady
Qualitative increase, cycle performance enhancing, capacitor still is able to retain original 79% or more after 10000 circle of circulation, coulombic efficiency still close to
98%.Electrode material after compound recombination increases 5 times compared to the operating voltage window of no compound recombination, compares existing one
The voltage window 0-0.4/0.6/0.7/0.8V of a little metal oxides also has a distinct increment.
Detailed description of the invention
Fig. 1 is the electrode material for super capacitor scanning electron microscope (SEM) photograph that step (4) obtains in present example 1；
Fig. 2 is electrification of the electrode material for super capacitor that step (4) obtains under different scanning rates in present example 1
Learn cyclic voltammetric performance map；
Fig. 3 is the electrode material for super capacitor AC impedance figure that step (4) obtains in present example 1；
Fig. 4 is circulation of the electrode material for super capacitor that step (4) obtains under 2A/g current density in present example 1
Capacitor retention rate and coulombic efficiency figure after 10000 circles；
Fig. 5 is that the supercapacitor primary electrode material that step (3) obtains is 0-0.2V in voltage window in present example 1
With the cyclic voltammogram scanned under 0-0.3V with sweep speed 50mV/s；
Fig. 6 is that the electrode material for super capacitor that step (4) obtains is 0-0.9V and 0- in voltage window in present example 1
The cyclic voltammogram scanned under 1.0V with sweep speed 50mV/s.
Specific embodiment
It elaborates below with reference to specific experiment process to present example, example described herein is used merely to solve
The present invention is released, is not intended to limit the present invention.Illustrate hereby.
Embodiment 1
It 1) is 1cm at size by foam nickel base material cutting2；Then the substrate completed will be cut and impregnate 30s in dilute hydrochloric acid,
It is cleaned repeatedly with deionized water again；The substrate after cleaning is finally placed in thermostatic drying chamber the freeze-day with constant temperature processing 4 at 60 DEG C
h。
2) using n-methyl-2-pyrrolidone as solvent, according to tin-antiomony oxide, holimium oxide and Kynoar (PVDF) quality
Tin-antiomony oxide/holimium oxide the weak solution for being 25mg/mL than the solution concentration for 8:1:1 preparation tin-antiomony oxide, holimium oxide, super
Middle removing 12h at 30 DEG C of sound washer；Using n-methyl-2-pyrrolidone as solvent, according to tin indium oxide, holimium oxide and gather inclined fluorine
Ethylene (PVDF) mass ratio is that 8:1:1 prepares tin indium oxide, the solution concentration of holimium oxide is the weak solution of 25mg/mL, in ultrasound
12h is removed at 30 DEG C in washer.
3) use range for the liquid-transfering needle of 0-10uL in fixing in 80 DEG C of baking ovens the base material of step 1) processing completion
It taking tin-antiomony oxide/holimium oxide weak solution to infuse uniformly note by several times to be added in foam nickel base, note plus time interval are 5min by several times,
Note dosage is 5uL every time, and altogether plus 40uL, amount containing tin-antiomony oxide is 1mg, wait infuse plus after the completion of in temperature be 80 DEG C of drying in oven
12h prepares tin-antiomony oxide/holimium oxide primary electrode material.
4) it takes tin indium oxide/holimium oxide weak solution uniformly to infuse by several times with liquid-transfering needle and is added on tin-antiomony oxide/holimium oxide primary
On electrode material, by several times note plus time interval be 5min, it is 2mg containing tin indium oxide altogether plus 80uL that infusing dosage every time, which is 5uL,
Wait infuse plus after the completion of temperature be 80 DEG C of drying in oven 12h, prepare tin-antiomony oxide/holimium oxide/tin indium oxide combination electrode material
Material.
Fig. 1 is the SEM figure for the combination electrode material that the embodiment obtains, and as seen from the figure, electrode material is in Nanoparticulate,
Hole or gap between different nanoclusters are conducive to electrode and soak and electrolyte ion discrepancy.
Fig. 2 is cyclic voltammogram of the obtained combination electrode material of the embodiment under different scanning rates, as seen from the figure,
Increase with sweep speed, the area that curve surrounds increases.Figure is trapezoidal in class, is in electric double layer capacitance.
Fig. 3 is the AC impedance figure for the combination electrode that the embodiment obtains, and as seen from the figure, is hardly visible half in high frequency region
Circle, shows that the impedance between electrode and electrode and electrolyte is smaller, and impedance slope is larger, and it is smaller to deviate vertical degree, table
Bright closer ideal capacitance.
Fig. 4 be the obtained combination electrode of the embodiment recycle under 2A/g current density after 10000 circles capacitor reservation and
Coulombic efficiency figure, as seen from the figure, electrode stability is preferable, and capacitor still is able to retain original 82%, coulomb after 10000 circle of circulation
Efficiency is still close to 100%.
It in voltage window is 0-0.2V that Fig. 5, which is the supercapacitor primary electrode material that obtains after the embodiment step (3),
With the cyclic voltammogram scanned under 0-0.3V with sweep speed 50mV/s, as seen from the figure, tin-antiomony oxide/holimium oxide primary electrical
Pole material is scanned in voltage window 0-0.2V is able to maintain complete electric double layer shape, carries out when increasing in 0-0.3V
When scanning, needle pattern is presented since excessively high voltage makes foam nickel base oxidation occur.
It in voltage window is 0-0.9V and 0- that Fig. 6, which is the electrode material for super capacitor that obtains after the embodiment step (4),
The cyclic voltammogram scanned under 1.0V with sweep speed 50mV/s；Tin-antiomony oxide/holimium oxide/the oxidation obtained as seen from the figure
Indium tin combination electrode material is able to maintain preferable electric double layer shape when voltage window is 0-0.9V, is 0- in voltage window
Still be able to keep complete electric double layer shape when 1.0V, this may be due in two oxides containing common element tin,
Increase Electron Transfer；This voltage range increases nearly 5 compared to the voltage window for the primary electrode material that step (3) obtain
Times, the voltage window 0-0.6/0.7/0.8V compared to existing most metals oxide also has a distinct increment.
Embodiment 2
It 1) is 1cm at size by foam nickel base material cutting2；Then the substrate completed will be cut and impregnate 15s in dilute hydrochloric acid,
It is cleaned repeatedly with deionized water again；The substrate after cleaning the freeze-day with constant temperature at 60 DEG C is finally placed in thermostatic drying chamber to handle
5h。
2) using n-methyl-2-pyrrolidone as solvent, according to tin-antiomony oxide, holimium oxide and Kynoar (PVDF) quality
Tin-antiomony oxide/holimium oxide the weak solution for being 15mg/mL than the solution concentration for 7:2:1 preparation tin-antiomony oxide, holimium oxide, super
12h is removed at 25 DEG C in sound washer；Using n-methyl-2-pyrrolidone as solvent, according to tin indium oxide, holimium oxide and gather inclined fluorine
Ethylene (PVDF) mass ratio is that 8:1:1 prepares tin indium oxide, the solution concentration of holimium oxide is the weak solution of 15mg/mL, in ultrasound
12h is removed at 30 DEG C in washer.
3) use range for the liquid-transfering needle of 0-10uL in fixing in 80 DEG C of baking ovens the base material of step 1) processing completion
Taking tin-antiomony oxide/holimium oxide solution, uniformly note is added in foam nickel base by several times, and note plus time interval are 5min by several times, every time
Infusing dosage is 10uL, is 2mg containing tin-antiomony oxide altogether plus 130uL, note plus after the completion of in temperature be 80 DEG C of drying in oven 12h,
Prepare tin-antiomony oxide/holimium oxide primary electrode material.
4) tin indium oxide/holimium oxide solution is taken uniformly to be added on tin-antiomony oxide/holimium oxide primary electrode by several times with liquid-transfering needle
On material, to infuse by several times plus time interval is 5min, the amount that note adds every time is 5uL, and altogether plus 65uL, amount containing tin indium oxide are 1mg, to
The drying in oven 12h for being 80 DEG C in temperature after the completion of adding is infused, tin-antiomony oxide/holimium oxide/tin indium oxide combination electrode material is prepared
Material.
Capacitor still is able to protect after the electrode obtained after the embodiment step (4) recycles 10000 circles under 2A/g current density
Original 80% is stayed, coulombic efficiency is still close to 98%；The combination electrode material is in sweep speed when voltage window is 0-1.0V
It still is able to keep good shape under 50mV/s.
Embodiment 3
It 1) is 1cm at size by foam nickel base material cutting2；Then the substrate completed will be cut and impregnate 20s in dilute hydrochloric acid,
It is cleaned repeatedly with deionized water again；The substrate after cleaning is finally placed in thermostatic drying chamber freeze-day with constant temperature at 50 DEG C and handles 6 h.
2) using n-methyl-2-pyrrolidone as solvent, according to the matter of tin-antiomony oxide, holimium oxide and Kynoar (PVDF)
Amount ratio is tin-antiomony oxide/holimium oxide weak solution that 6:3:1 prepares tin-antiomony oxide, the solution concentration of holimium oxide is 20mg/mL,
12h is removed at 35 DEG C in ultrasonic cleaning machine；Using n-methyl-2-pyrrolidone as solvent, according to tin indium oxide, holimium oxide and gather inclined
The mass ratio of vinyl fluoride (PVDF) is that 6:3:1 prepares tin indium oxide, the solution concentration of holimium oxide is the weak solution of 20mg/mL,
Ultrasound removing 12h at 25 DEG C.
3) base material of step 1) processing completion is taken in fixing in 70 DEG C of baking ovens with the liquid-transfering needle that range is 0-10uL
Uniformly note is added in foam nickel base the gradation of tin-antiomony oxide/holimium oxide weak solution, and the time interval that note adds by several times is 10min,
The amount that each note adds is 10uL, and altogether plus 150uL, the amount containing tin-antiomony oxide are 3mg, the baking for being 80 DEG C in temperature after the completion of infusing and adding
12h is dried in case, prepares tin-antiomony oxide/holimium oxide primary electrode material.
4) it takes the weak solution of tin indium oxide to infuse by several times with liquid-transfering needle and is added on tin-antiomony oxide/holimium oxide primary electrode material
On, by several times note plus time interval be 5min, every time note plus amount be 5uL, be 0.5mg containing tin indium oxide, wait infuse altogether plus 25uL
The drying in oven 12h for being 80 DEG C in temperature after the completion of adding, prepares tin-antiomony oxide/holimium oxide/tin indium oxide combination electrode material.
Capacitor still is able to protect after the electrode obtained after the embodiment step (4) recycles 10000 circles under 2A/g current density
Original 86% is stayed, coulombic efficiency is still close to 98%；The combination electrode material is in sweep speed when voltage window is 0-0.7V
It still is able to keep good shape under 50mV/s.
Embodiment 4
It 1) is 1cm at size by foam nickel base material cutting2；Then the substrate completed will be cut and impregnate 30s in dilute hydrochloric acid,
It is cleaned repeatedly with deionized water again；The substrate after cleaning is finally placed in thermostatic drying chamber freeze-day with constant temperature at 40 DEG C and handles 5 h.
2) using n-methyl-2-pyrrolidone as solvent, according to tin-antiomony oxide, holimium oxide and Kynoar (PVDF) quality
Tin-antiomony oxide/holimium oxide the weak solution for being 25mg/mL than the solution concentration for 8:1:1 preparation tin-antiomony oxide, holimium oxide, super
12h is removed at 35 DEG C in sound washer；Using n-methyl-2-pyrrolidone as solvent, according to tin indium oxide, holimium oxide and gather inclined fluorine
The mass ratio of ethylene (PVDF) is that 7:2:1 prepares tin indium oxide, the solution concentration of holimium oxide is the weak solution of 25mg/mL, super
12h is removed at 30 DEG C in sound washer.
3) base material for completing step 1) processing is in fixed in 60 DEG C of baking oven, the liquid-transfering needle for being 0-10uL with range
Taking the gradation of tin-antiomony oxide/holimium oxide solution, uniformly note is added in foam nickel base, and the time interval that note adds by several times is 5min, often
The amount that secondary note adds is 5uL, and altogether plus 40uL, amount containing tin-antiomony oxide are 1mg, is dried in the baking oven that temperature is 80 DEG C after the completion of infusing and adding
Dry 12h, prepares tin-antiomony oxide/holimium oxide primary electrode material.
4) it takes the solution of tin indium oxide uniformly to infuse by several times with liquid-transfering needle and is added on tin-antiomony oxide/holimium oxide primary electrode material
On, note plus time interval are 5min by several times, and infusing dosage every time is 10uL, and altogether plus 80uL, amount containing tin indium oxide are 2mg, are added wait infuse
The drying in oven 12h for being after the completion 70 DEG C in temperature, prepares tin-antiomony oxide/holimium oxide/tin indium oxide combination electrode material.
Capacitor still is able to protect after the electrode obtained after the embodiment step (4) recycles 10000 circles under 2A/g current density
Original 79% is stayed, coulombic efficiency is still close to 100%；The combination electrode material is in sweep speed when voltage window is 0-1.0V
It still is able to keep good shape under 50mV/s.
Embodiment 5
It 1) is 1cm at size by foam nickel base material cutting2；Then the substrate completed will be cut and impregnate 20s in dilute hydrochloric acid,
It is cleaned repeatedly with deionized water again；The substrate after cleaning is finally placed in thermostatic drying chamber freeze-day with constant temperature at 60 DEG C and handles 4 h.
2) using n-methyl-2-pyrrolidone as solvent, according to the matter of tin-antiomony oxide, holimium oxide and Kynoar (PVDF)
Amount ratio is tin-antiomony oxide/holimium oxide weak solution that 7:2:1 prepares tin-antiomony oxide, the solution concentration of holimium oxide is 25mg/mL,
12h is removed at 30 DEG C in ultrasonic cleaning machine；Using n-methyl-2-pyrrolidone as solvent, according to tin indium oxide, holimium oxide and gather inclined
The mass ratio of vinyl fluoride (PVDF) is that 6:3:1 prepares tin indium oxide, the solution concentration of holimium oxide is the weak solution of 25mg/mL,
12h is removed at 35 DEG C in ultrasonic cleaning machine.
3) base material for completing step 1) processing is in fixed in 70 DEG C of baking oven, the liquid-transfering needle for being 0-10uL with range
Taking the gradation of tin-antiomony oxide/holimium oxide solution, uniformly note is added in foam nickel base, is divided into 5min between being infused between adding by several times, every time
Note plus amount be 10uL, be 2mg containing tin-antiomony oxide altogether plus 80uL, wait infuse plus after the completion of in temperature be 80 DEG C of drying in oven
12h prepares tin-antiomony oxide/holimium oxide primary electrode material.
4) it takes the weak solution of tin indium oxide uniformly to infuse by several times with liquid-transfering needle and is added on tin-antiomony oxide/holimium oxide primary electrode material
On, note plus time interval are 5min by several times, every time note plus amount be 5uL, altogether plus 40uL, be 1mg containing tin indium oxide, added wait infuse
After temperature be 80 DEG C of drying in oven 12h, prepare tin-antiomony oxide/holimium oxide/tin indium oxide combination electrode material.
Capacitor still is able to protect after the electrode obtained after the embodiment step (4) recycles 10000 circles under 2A/g current density
Original 80% is stayed, coulombic efficiency is still close to 98%；The combination electrode material is in sweep speed when voltage window is 0-0.9V
It still is able to keep good shape under 50mV/s.
Embodiment 6
It 1) is 1cm at size by foam nickel base material cutting2；Then the substrate completed will be cut and impregnate 30s in dilute hydrochloric acid,
It is cleaned repeatedly with deionized water again；The substrate after cleaning is finally placed in thermostatic drying chamber freeze-day with constant temperature at 60 DEG C and handles 4 h.
2) using n-methyl-2-pyrrolidone as solvent, according to tin-antiomony oxide, holimium oxide and Kynoar (PVDF) quality
Than for 6:3:1 prepare liquor capacity be 5mL, tin-antiomony oxide/holimium oxide weak solution that concentration is 15mg/mL, in 35 DEG C of ultrasounds
The lower removing 12h of cleaning action；Using n-methyl-2-pyrrolidone as solvent, according to tin indium oxide, holimium oxide and Kynoar
(PVDF) mass ratio be 8:1:1 prepare liquor capacity be 5mL, the weak solution for the tin indium oxide that concentration is 15mg/mL, in ultrasound
12h is removed at 25 DEG C in washer.
3) base material that step 1) is handled well is suspended vacantly in 60 DEG C of baking oven, the liquid relief for being 0-10uL with range
Needle takes tin-antiomony oxide/holimium oxide weak solution, and uniformly note is added in foam nickel base by several times, and note plus time interval are 5min by several times,
Each amount added of infusing is 10uL, and altogether plus 200uL, amount containing tin-antiomony oxide are 3mg, in temperature in 80 DEG C of baking ovens after the completion of infusing and adding
12h is dried, tin-antiomony oxide/holimium oxide primary electrode material is prepared.
4) it takes the weak solution of tin indium oxide uniformly to infuse by several times with liquid-transfering needle and is added on tin-antiomony oxide/holimium oxide primary electrode material
On, it infuses by several times plus time interval is 5min, the amount that note adds every time is 10uL, and altogether plus 30uL, amount containing tin indium oxide are 0.5mg, to
Note plus after the completion of temperature be 80 DEG C of drying in oven 12h, prepare tin-antiomony oxide/holimium oxide/tin indium oxide combination electrode material.
Capacitor still is able to protect after the electrode obtained after the embodiment step (4) recycles 10000 circles under 2A/g current density
Original 83% is stayed, coulombic efficiency is still close to 100%；The combination electrode material is in sweep speed when voltage window is 0-0.6V
It still is able to keep good shape under 50mV/s.
The foregoing is only a preferred embodiment of the present invention, not does restriction in any form to the present invention.It is all
Any equivalent variation that those skilled in the art makes above-described embodiment using technical solution of the present invention is modified or is drilled
Become etc., all of which are still within the scope of the technical scheme of the invention.
Claims (9)
1. a kind of supercapacitor tin-antiomony oxide/holimium oxide/tin indium oxide combination electrode material preparation method, feature exist
In, comprising the following steps:
(1) base material pre-processes
Firstly, substrate is impregnated in dilute hydrochloric acid, then cleaned repeatedly with deionized water；Then the substrate after cleaning is subjected to constant temperature
It is dried；
(2) tin-antiomony oxide/holimium oxide and tin indium oxide/holimium oxide solution are prepared
Tin-antiomony oxide, holimium oxide and Kynoar are mixed and are dissolved in solvent, solution A is obtained；By solution A under ultrasonication
Ultrasound removing dispersion；Tin indium oxide, holimium oxide and Kynoar are mixed and are dissolved in solvent, solution B is obtained；In ultrasonication
Lower remove solution B ultrasound is dispersed；
(3) tin-antiomony oxide/holimium oxide/tin indium oxide combination electrode material is prepared
Taking solution A, note is added on through in step (1) treated substrate by several times, wait infuse plus after the completion of be dried, obtain tin oxide
Antimony/holimium oxide primary electrode material；Taking solution B, note is added on tin-antiomony oxide/holimium oxide primary electrode material by several times, adds into wait infuse
After be dried, obtain the tin-antiomony oxide/holimium oxide/tin indium oxide combination electrode material.
2. preparation method according to claim 1, which is characterized in that in the step (1), the substrate be nickel foam or
Foam copper.
3. preparation method according to claim 1, which is characterized in that in the step (1), soaking time 10-60s,
Drying temperature is 40-60 DEG C, and drying time is 2-6 h.
4. preparation method according to claim 1, which is characterized in that in the step (2), tin-antiomony oxide in solution A,
Holimium oxide and Kynoar mass ratio are 6-8:1-3:1, tin indium oxide, holimium oxide and Kynoar mass ratio in solution B
For 6-8:1-3:1；The mass concentration of tin-antiomony oxide and holimium oxide in solution A is 10-25mg/mL, tin indium oxide and holimium oxide
Mass concentration in solution B is 10-25mg/mL.
5. preparation method according to claim 1, which is characterized in that in the step (2), the ultrasound of solution A and solution B
Splitting time is 7-12h.
6. preparation method according to claim 1, which is characterized in that in the step (3), infuse the time interval added by several times
For 3-10min, drying time is 4-12h after the completion of note adds, and drying temperature is 50-80 DEG C.
7. preparation method according to claim 1, which is characterized in that in the step (2), solvent is in solution A and B
NMP。
8. preparation method according to claim 1, which is characterized in that the body of note adds in step (4) solution A and solution B
Product is than being 1:1-7:1.
9. the supercapacitor tin-antiomony oxide/holimium oxide/oxidation that any one of the claim 1-8 preparation method obtains
Indium tin combination electrode material.
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