CN108447702A - A kind of high circulation service life rGO-CeO2The preparation of/PorousPANI ternary composite electrode materials - Google Patents
A kind of high circulation service life rGO-CeO2The preparation of/PorousPANI ternary composite electrode materials Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000011206 ternary composite Substances 0.000 title claims abstract description 11
- 229920000767 polyaniline Polymers 0.000 claims abstract description 88
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 58
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims description 35
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000003599 detergent Substances 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000002848 electrochemical method Methods 0.000 claims description 4
- 238000013459 approach Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 230000005518 electrochemistry Effects 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000003701 mechanical milling Methods 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 11
- 229910021389 graphene Inorganic materials 0.000 abstract description 8
- 239000003990 capacitor Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000002322 conducting polymer Substances 0.000 description 4
- 229920001940 conductive polymer Polymers 0.000 description 4
- 230000003111 delayed effect Effects 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 229960002050 hydrofluoric acid Drugs 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- -1 transition metal (hydrogen) oxide Chemical class 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 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
- H01G11/84—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
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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
- 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)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention belongs to ultracapacitor field, the preparation of the especially a kind of graphene/ceria in high circulation service life/porous polyaniline ternary composite electrode material.The present invention is shorter primarily directed to existing electrode material for super capacitor cycle life, the fast disadvantage of capacity loss.A kind of simple and effective rGO CeO are provided2/ Porous PANI electrode materials and preparation method thereof, synthesize CeO by mechanical lapping first2/ Porous PANI, then rGO CeO are made by electrochemical reduction method2/ Porous PANI ternary composite electrode materials.When the mass ratio of ceria and porous polyaniline is 1:When 4, which is 5A.g in current density‑1The lower capacitance reserved after 10000 cycles still may be up to 70.23%.
Description
Technical field
The present invention relates to a kind of rGO-CeO of high circulation service life2/ Porous PANI tri compound super capacitors
The preparation of device electrode material.
Background technology
Ultracapacitor be grow up from the 1970s and 1980s in last century by polarized electrolytic matter come a kind of electricity of energy storage
Chemical component.It is different from traditional electrochmical power source, be it is a kind of between traditional capacitor and battery, with property
Power supply relies primarily on electric double layer and Redox pseudocapacitance charge storage electric energy.Ultracapacitor with its large capacity, high power,
The superior performance such as long-life, of low cost, environmental-friendly can partly or entirely substitute traditional chemical cell, and have
There is purposes more extensive than traditional chemical cell.The technology of super capacitor continues to develop, and pushes its application range from initial
Electronic device field expand to dynamic field, energy storage field.The mankind also exist while making great efforts to explore and develop the new energy
New energy storage technology is constantly improved, ultracapacitor is as outstanding person therein, the performance of new type power energy resource system
Extremely excellent performance is gone out, there is very vast potential for future development.The core of ultracapacitor be on electrode and electrolyte,
Wherein the factors such as electrode material specific surface area, conductivity, pore size, pattern, structure, acid-fast alkali-proof directly determine super
Capacitor chemical property.Common electrode material includes carbon material, conducting polymer, transition metal (hydrogen) oxide, wherein
Carbon-based material large specific surface area, electric conductivity are high, stability is good, but its chemical property is not very ideal;Single conduction is poly-
Highdensity charge can be stored by closing object electrode material, generate big faraday's capacitance, but this kind of mechanical property of materials is bad, long
Phase cyclical stability is poor, and operating voltage and energy storage density are to be improved;Metal oxide has attracted extensive concern because of its high power capacity.
Prepared ternary electrode material has had both carbon material, conducting polymer and transiting metal oxidation in the present invention
Object.Wherein, each material separately as electrode material when have the following deficiencies place, including to be one kind have (1) graphene
Many excellent properties, such as novel carbon-based electrode material of good conduction, heat conduction, large specific surface area.But due to graphene sheet layer
Between strong π-π effects cause its surface to be easy to the service life that largely reduced it as electrode material of reuniting.(2) numerous
Conducting polymer in polyaniline capacitance is high, resistance is low, be simply easy to polymerization in the solution and prepare, but polyaniline is as electricity
The shortcomings that pole material is that its cyclical stability is poor, and capacity loss is fast.(3) metal oxide, which is used as electrode material, has than carbon materials
Material and the higher energy density of polymer and cycle life.Wherein CeO2Due to its cation can+3 and+4 valence oxidation state it
Between convert and receive notable concern, and due to CeO2Ability with reversible release oxygen, can serve as oxygen buffer.But
CeO2Electric conductivity causes its capacitance low not as good as carbon material and polymer, and resistance is high.Therefore, the present invention is directed to prepare a kind of fusion
Several electrode material advantages are in the novel ternary composite electrode material haveing excellent performance of one.
Invention content
The present invention mainly solve (1) graphene surface be easy to reunite, by with metal oxide CeO2And conducting polymer
Compound its surface agglomeration that can alleviate of object PANI is to overcome this disadvantage;(2) although polyaniline capacitance is higher, its
Cyclical stability is poor, by with CeO2The compound cycle life that can significantly improve compound rear electrode material.(3) oxo transition metal
Compound CeO2Poorly conductive, by with the graphene and polyaniline of excellent electric conductivity are compound makes up CeO2In terms of electric conductivity
Defect.RGO-CeO prepared by the present invention2/ Porous PANI electrode materials be both utilized graphene, polyaniline, ceria it
Between respective advantage make up mutual disadvantage, to make trielement composite material being optimal of performance;Graphite is utilized again
The synergistic effect generated between alkene, polyaniline, ceria, to obtain a kind of high circulation service life rGO-CeO2/Porous
PANI electrode material for super capacitor.
A kind of high circulation service life rGO-CeO of the present invention2The preparation of/Porous PANI ternary composite electrode materials be by
Following steps carry out:
(1) by 20ml 0.2mol L-1Cerous nitrate solution and 15ml 3.0mol L-1Urea mixes, and what is be vigorously stirred is same
When be added dropwise ammonia spirit tune pH value, 80 DEG C of constant temperature 2h, and 12h is settled in room temperature;Then it is filtered, washed.The precipitation of gained
60 DEG C of 5h of constant temperature in insulating box, then 1h is burnt in 400 DEG C of Muffle furnaces, CeO is made2;
(2) in 40mL 0.5mol L-1Sulfuric acid in be added 0.5mL aniline solution, add 0.25g detergent alkylates
Sodium sulfonate ultrasonic mixing is uniform, is labeled as No. 1 reagent;In 0.5mol L-1Sulfuric acid in a certain amount of ATP is added 4g/100mL is made
Solution.It takes above-mentioned solution 38mL and No. 1 reagent is added and be uniformly mixed, be labeled as No. 3 reagents;No. 3 reagents are put in ice-water bath
Middle stirring;In 18mL 0.5mol L-1Sulfuric acid in be added 1.25g ammonium persulfate, be labeled as No. 2 reagents;No. 2 reagents are delayed
Slow to be added dropwise to No. 3 reagents, the composite material of ATP/PANI is made in abundant polymerisation 8h;Weigh 0.8g ATP/PANI, 4g hydrogen
Fluoric acid mixes simultaneously magnetic agitation 11h, then is filtered with deionized water, washing, and naturally dry forms Porous PANI;
(3) by Porous PANI and CeO2According to the compound preparation CeO of ad hoc approach2/ Porous PANI compounds;
(4) certain density CeO is prepared respectively2/ Porous PANI, GO dispersion liquids, liquid-transfering gun first pipette certain volume
CeO2/ Porous PANI dispersant liquid drops are added on glass-carbon electrode after natural drying, then pipette same volume GO dispersion liquids, natural
It dries to obtain GO-CeO2/ Porous PANI, electrochemical method restore to obtain rGO-CeO2/Porous PANI。
Positive effect obtained by the present invention is:(1) when preparing polyaniline using chemical oxidization method in-situ polymerization
ATP is added as template, then template is gone to obtain multi-pore channel, the increased porous polyaniline of specific surface area has as electrode material
Conducive to electron-transport and mass transfer to improve trielement composite material rGO-CeO2The capacitance and cycle of/Porous PANI
Service life.(2)CeO2The whole cyclical stability of raising, but its poorly conductive are mainly played in trielement composite material, are needed
This defect is made up by adulterating or loading the substance of excellent electric conductivity.It selects in the present invention and is easy under protonic acid doping
The chain polymer Porous PANI of polymerization, the characteristics of being easily supported due to it, by CeO2Particulate load improves thereon
CeO2And the overall conductivity of composite material.(3) by testing, the rGO-CeO under optimal proportion2/ Porous PANI are in electric current
Density is 5.0A g-1The lower capacitance maintenance dose after 10000 cycles compares CeO still up to 70.23%2、CeO2/Porous
PANI cyclical stabilities are much higher.
Description of the drawings
Fig. 1 is rGO-CeO2The scanning electron microscope (SEM) photograph of/Porous PANI.
Fig. 2 is different proportion rGO-CeO2The cyclic voltammogram of/Porous PANI.
Fig. 3 is CeO2、CeO2/Porous PANI、rGO-CeO2The cycle life figure of/Porous PANI.
Specific implementation mode
Specific implementation mode one:A kind of high circulation service life rGO-CeO of present embodiment2/ Porous PANI tri compounds
The preparation of electrode material is to carry out according to the following steps:
(1) by 20ml 0.2mol L-1Cerous nitrate solution and 15ml 3.0mol L-1Urea mixes, and what is be vigorously stirred is same
When be added dropwise ammonia spirit tune pH value, 80 DEG C of constant temperature 2h, and 12h is settled in room temperature;Then it is filtered, washed.The precipitation of gained
60 DEG C of 5h of constant temperature in insulating box, then 1h is burnt in 400 DEG C of Muffle furnaces, CeO is made2;
(2) in 40mL 0.5mol L-1Sulfuric acid in be added 0.5mL aniline solution, add 0.25g detergent alkylates
Sodium sulfonate ultrasonic mixing is uniform, is labeled as No. 1 reagent;In 0.5mol L-1Sulfuric acid in a certain amount of ATP is added 4g/100mL is made
Solution.It takes above-mentioned solution 38mL and No. 1 reagent is added and be uniformly mixed, be labeled as No. 3 reagents;No. 3 reagents are put in ice-water bath
Middle stirring;In 18mL 0.5mol L-1Sulfuric acid in be added 1.25g ammonium persulfate, be labeled as No. 2 reagents;No. 2 reagents are delayed
Slow to be added dropwise to No. 3 reagents, the composite material of ATP/PANI is made in abundant polymerisation 8h;Weigh 0.8g ATP/PANI, 4g hydrogen
Fluoric acid mixes simultaneously magnetic agitation 11h, then is filtered with deionized water, washing, and naturally dry forms Porous PANI;
(3) by Porous PANI and CeO2According to the compound preparation CeO of ad hoc approach2/ Porous PANI compounds;
(4) certain density CeO is prepared respectively2/ Porous PANI, GO dispersion liquids, liquid-transfering gun first pipette certain volume
CeO2/ Porous PANI dispersant liquid drops are added on glass-carbon electrode after natural drying, then pipette same volume GO dispersion liquids, natural
It dries to obtain GO-CeO2/ Porous PANI, electrochemical method restore to obtain rGO-CeO2/Porous PANI。
Specific implementation mode two:The present embodiment is different from the first embodiment in that step (3) passes through mechanical lapping
4h prepares CeO2/Porous PANI.Other are same as the specific embodiment one.
Specific implementation mode three:The present embodiment is different from the first and the second embodiment in that m in step (3)CeO2:
mPorous PANIIt is 1:4、1:2、 1:1、2:1、4:1.Other are the same as one or two specific embodiments.
Specific implementation mode four:Present embodiment step (4) unlike specific implementation mode one to three prepares concentration
For 2mg/mL, it is 5 μ L to pipette volume.
A kind of high circulation service life rGO-CeO is illustrated by following embodiment and comparative example2/ Porous PANI ternarys
The preparation of combination electrode material:
Embodiment one:
(1) by 20ml 0.2mol L-1Cerous nitrate solution and 15ml 3.0mol L-1Urea mixes, and what is be vigorously stirred is same
When be added dropwise ammonia spirit tune pH value, 80 DEG C of constant temperature 2h, and 12h is settled in room temperature;Then it is filtered, washed.The precipitation of gained
60 DEG C of 5h of constant temperature in insulating box, then 1h is burnt in 400 DEG C of Muffle furnaces, CeO is made2;
(2) in 40mL 0.5mol L-1Sulfuric acid in be added 0.5mL aniline solution, add 0.25g detergent alkylates
Sodium sulfonate ultrasonic mixing is uniform, is labeled as No. 1 reagent;In 0.5mol L-1Sulfuric acid in a certain amount of ATP is added 4g/100mL is made
Solution.It takes above-mentioned solution 38mL and No. 1 reagent is added and be uniformly mixed, be labeled as No. 3 reagents;No. 3 reagents are put in ice-water bath
Middle stirring;In 18mL 0.5mol L-1Sulfuric acid in be added 1.25g ammonium persulfate, be labeled as No. 2 reagents;No. 2 reagents are delayed
Slow to be added dropwise to No. 3 reagents, the composite material of ATP/PANI is made in abundant polymerisation 8h;Weigh 0.8g ATP/PANI, 4g hydrogen
Fluoric acid mixes simultaneously magnetic agitation 11h, then is filtered with deionized water, washing, and naturally dry forms Porous PANI;
(3) by Porous PANI and CeO2According to 1:4、1:2、1:1、2:1、4:1 mass prepares CeO than mechanical lapping 4h2/
Porous PANI compounds;
(4) CeO that concentration is 2mg/mL is prepared respectively2/ Porous PANI, GO dispersion liquids, liquid-transfering gun first pipette 5 μ L
CeO2/ Porous PANI dispersant liquid drops are added on glass-carbon electrode after natural drying, then pipette same volume GO dispersion liquids, natural
It dries to obtain GO-CeO2/ Porous PANI, electrochemical method restore to obtain rGO-CeO2/Porous PANI。
Fig. 1 is rGO-CeO2The SEM of/Porous PANI schemes.It can be seen that graphene oxide graphite after electrochemical reduction
Fold layer structure is presented in alkene, and has CeO2Little particle is sporadicly supported on Porous PANI and graphene, the tri compound material
Expect rGO-CeO2/ Porous PANI are in integrally the alternate dendritic morphology of light and shade.
Fig. 2 is different proportion rGO-CeO2The CV of/Porous PANI schemes.CV figures, which are shown, to be shown to work as CeO2With Porous
PANI mass ratioes are 1:When 4, the redox peak current and peak integral area of composite material are all maximum, illustrate the mass ratio
Composite material charge storage capacity is best, and capacity is maximum, and chemical property is best.
Fig. 3 is CeO2、CeO2/Porous PANI、rGO-CeO2The cycle life figures of/Porous PANI.In 0.5mol
L-1H2SO4CeO in solution2、CeO2/ Porous PANI and rGO-CeO2Between the specific capacitance and cycle-index of/Porous PANI
Relationship, using 5A g-1And carry out the cycle life test of 10000 circles, final result CeO2Capacitance be left 45.45%,
CeO2The capacitance of/Porous PANI is left 59.48%, however rGO-CeO2The capacitance of/Porous PANI is left
70.23%.Illustrate rGO-CeO2CeO of/Porous PANI the composite materials compared to unitary2, binary CeO2-Porous
The cycle life that PANI is more longlasting, stablizes.
Comparative example one:
(1) by 20ml 0.2mol L-1Cerous nitrate solution and 15ml 3.0mol L-1Urea mixes, and what is be vigorously stirred is same
When be added dropwise ammonia spirit tune pH value, 80 DEG C of constant temperature 2h, and 12h is settled in room temperature;Then it is filtered, washed.The precipitation of gained
60 DEG C of 5h of constant temperature in insulating box, then 1h is burnt in 400 DEG C of Muffle furnaces, CeO is made2;
Comparative example two:
(1) by 20ml 0.2mol L-1Cerous nitrate solution and 15ml 3.0mol L-1Urea mixes, and what is be vigorously stirred is same
When be added dropwise ammonia spirit tune pH value, 80 DEG C of constant temperature 2h, and 12h is settled in room temperature;Then it is filtered, washed.The precipitation of gained
60 DEG C of 5h of constant temperature in insulating box, then 1h is burnt in 400 DEG C of Muffle furnaces, CeO is made2;
(2) in 40mL 0.5mol L-1Sulfuric acid in be added 0.5mL aniline solution, add 0.25g detergent alkylates
Sodium sulfonate ultrasonic mixing is uniform, is labeled as No. 1 reagent;In 0.5mol L-1Sulfuric acid in a certain amount of ATP is added 4g/100mL is made
Solution.It takes above-mentioned solution 38mL and No. 1 reagent is added and be uniformly mixed, be labeled as No. 3 reagents;No. 3 reagents are put in ice-water bath
Middle stirring;In 18mL 0.5mol L-1Sulfuric acid in be added 1.25g ammonium persulfate, be labeled as No. 2 reagents;No. 2 reagents are delayed
Slow to be added dropwise to No. 3 reagents, the composite material of ATP/PANI is made in abundant polymerisation 8h;Weigh 0.8g ATP/PANI, 4g hydrogen
Fluoric acid mixes simultaneously magnetic agitation 11h, then is filtered with deionized water, washing, and naturally dry forms Porous PANI;
(3) by Porous PANI and CeO2According to 4:1 mass prepares CeO than mechanical lapping 4h2/ Porous PANI are compound
Object.
Claims (5)
1. a kind of high circulation service life rGO-CeO2The preparation of/Porous PANI ternary composite electrode materials, it is characterised in that ternary
Electrode material is to carry out according to the following steps:
(1) by 20ml 0.2mol L-1Cerous nitrate solution and 15ml 3.0mol L-1Urea mixes, while being vigorously stirred by
Ammonia spirit tune pH value, 80 DEG C of constant temperature 2h are added dropwise to, and 12h is settled in room temperature;Then it is filtered, washed.Gained is deposited in perseverance
60 DEG C of 5h of constant temperature in incubator, then 1h is burnt in 400 DEG C of Muffle furnaces, CeO is made2;
(2) in 40mL 0.5mol L-1Sulfuric acid in be added 0.5mL aniline solution, add the detergent alkylate sulphur of 0.25g
Sour sodium ultrasonic mixing is uniform, is labeled as No. 1 reagent;In 0.5mol L-1Sulfuric acid in a certain amount of ATP be added be made 4g/100mL's
Solution.It takes above-mentioned solution 38mL and No. 1 reagent is added and be uniformly mixed, be labeled as No. 3 reagents;No. 3 reagents are put in ice-water bath
Stirring;In 18mL 0.5mol L-1Sulfuric acid in be added 1.25g ammonium persulfate, be labeled as No. 2 reagents;No. 2 reagents are slow
No. 3 reagents are added dropwise to, the composite material of ATP/PANI is made in abundant polymerisation 8h;Weigh 0.8gATP/PANI, 4g hydrogen fluorine
Acid mixes simultaneously magnetic agitation 11h, then is filtered with deionized water, washing, and naturally dry forms porous PANI;
(3) by porous PANI and CeO2According to the compound preparation CeO of ad hoc approach2/ porous PANI compounds;
(4) certain density CeO is prepared respectively2/ porous PANI, GO dispersion liquids, liquid-transfering gun first pipette certain volume CeO2/
Porous PANI dispersant liquid drops are added on glass-carbon electrode after natural drying, then pipette same volume GO dispersion liquids, and naturally dry obtains
To GO-CeO2/ porous PANI, electrochemical method restore to obtain rGO-CeO2/porous PANI。
2. a kind of high circulation service life rGO-CeO according to claim 12/ Porous PANI ternary composite electrode materials
It prepares, it is characterised in that step (3) grinds 4h using mechanical milling method.
3. a kind of high circulation service life rGO-CeO according to claim 12/ Porous PANI ternary composite electrode materials
It prepares, it is characterised in that step (3) mCeO2:mPorous PANIIt is 1:4、1:2、1:1、2:1、4:1.
4. a kind of high circulation service life rGO-CeO according to claim 12/ Porous PANI ternary composite electrode materials
It prepares, it is characterised in that step (4) prepares a concentration of 2mg/mL, and it is 5 μ L to pipette volume.
5. a kind of high circulation service life rGO-CeO according to claim 12/ Porous PANI ternary composite electrode materials
It prepares, it is characterised in that its capacitance maintenance dose still may be up to 70.23% after 10000 electrochemistry cycles.
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