CN110349760A - A kind of pomelo peel carbon and high molecular polymer combination electrode and the preparation method and application thereof - Google Patents
A kind of pomelo peel carbon and high molecular polymer combination electrode and the preparation method and application thereof Download PDFInfo
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- CN110349760A CN110349760A CN201910616440.2A CN201910616440A CN110349760A CN 110349760 A CN110349760 A CN 110349760A CN 201910616440 A CN201910616440 A CN 201910616440A CN 110349760 A CN110349760 A CN 110349760A
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- pomelo peel
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- high molecular
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- 240000000560 Citrus x paradisi Species 0.000 title claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 23
- 229920000642 polymer Polymers 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003610 charcoal Substances 0.000 claims abstract description 19
- 229920000767 polyaniline Polymers 0.000 claims abstract description 13
- 238000002484 cyclic voltammetry Methods 0.000 claims abstract description 8
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 8
- 229920000123 polythiophene Polymers 0.000 claims abstract description 8
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 7
- 239000012528 membrane Substances 0.000 claims abstract description 7
- 239000002002 slurry Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920000557 Nafion® Polymers 0.000 claims abstract description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 5
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 3
- 229910021397 glassy carbon Inorganic materials 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 9
- 238000004070 electrodeposition Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- 244000276331 Citrus maxima Species 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 9
- 238000011161 development Methods 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910015900 BF3 Inorganic materials 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000002322 conducting polymer Substances 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000002847 impedance measurement Methods 0.000 description 2
- MINVSWONZWKMDC-UHFFFAOYSA-L mercuriooxysulfonyloxymercury Chemical compound [Hg+].[Hg+].[O-]S([O-])(=O)=O MINVSWONZWKMDC-UHFFFAOYSA-L 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910000370 mercury sulfate Inorganic materials 0.000 description 2
- 229910000371 mercury(I) sulfate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical group 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 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
-
- 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
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a kind of pomelo peel carbon and high molecular polymer combination electrode and the preparation method and application thereof, are related to electrode material;The preparation method, the following steps are included: pomelo peel Carbon Materials are uniformly mixed to obtain slurry with nafion solution, dehydrated alcohol, slurry is evenly coated in again the glassy carbon electrode surface pre-processed, is placed in drier dry 12h, obtains the electrode for being covered with uniform pomelo peel carbon membrane;The electrode is subjected to electrochemical copolymerization with polyaniline, polythiophene and polypyrrole respectively using cyclic voltammetry again, obtains the combination electrode of pomelo peel charcoal from different polymer.
Description
Technical field
The present invention relates to electrode material, especially a kind of pomelo peel carbon and high molecular polymer combination electrode and its preparation side
Method and application.
Background technique
It is also more next to the consumption of the energy with the progress of science and technology, the development and population sharp increase of social economy
Bigger, the exhausted an urgent demand renewable resource of non-renewable resources plays its substitution effect, while requiring to non-renewable money
Sustainable, the effective use in source, give full play to its potential.Existing traditional energy system also can no longer meet modern industry,
The demand of the development such as agricultural, forestry, fuel oil and coal resource are not only non-renewable, can also generate in using consumption process a large amount of
The harmful substances such as CO2, SO2, bring very serious environmental pollution.This just promote people more pay attention to establishing it is new, effective
Energy supply system, to guarantee economic sustainable growth, while can also be helpful to protection environment.Wherein, it taps a new source of energy
Currently to solve the problems, such as this most efficient method with renewable and clean energy resource, be the key technology that must solve 21 century it
One, new energy materials are then basis and the core realized the development and utilization of new energy, and support its development.
Battery industry is an important component of field of new energy applications, because electric energy is as the final of energy utilization
Existence form has become human being's production and the indispensable driving source of social development.First to the exploitation people of electrical source of power
What is expected is exactly to possess the lithium ion battery of high-energy density, but when lithium electricity is as electrical source of power, there is one apparent to lack
Point is exactly that power density is smaller, so that it cannot meet the needs of high power discharge, this defect, which has become, limits its development
Major obstacle.Thus it is possible to the supercapacitor of fast charging and discharging becomes new research hotspot, but supercapacitor
Charge storage density is too low, it is made not power for a long time, limits its application prospect as electrical source of power.
Supercapacitor is a kind of device between traditional capacitor and rechargeable battery, it have fast charging and discharging,
The features such as environmental-friendly, high power density, overlength cycle life, wide pollution-free and operating temperature range.Currently, mainly there is metal
Oxide, conducting polymer, active carbon material and many doping type composite materials are used as its electrode material.Activated carbon is as electricity
The capacitor research history of pole material is longer, and technology is also most mature, but its production technology is complicated, the production cycle is long, and capacity
It is universal all relatively low, limit the application of supercapacitor.
In recent years, miniaturization, portable and wearable electronic product are increasingly becoming development trend.For that can stretch
Contracting, flexible, foldable electronic device, also need have electrochemical energy storage device flexible.Conducting high polymers object
And its research of various composite materials and preparation are increasingly becoming current hot spot.
Summary of the invention
The present invention is intended to provide a kind of pomelo peel carbon and high molecular polymer combination electrode and preparation method and application.
To achieve the above object, technical solution provided by the invention is such that a kind of pomelo peel carbon and high molecular polymerization
The preparation method of object combination electrode, comprising the following steps:
Pomelo peel Carbon Materials are uniformly mixed into obtain slurry with nafion solution, dehydrated alcohol, then slurry is uniformly applied
In the glassy carbon electrode surface pre-processed, it is placed in drier dry 12h, obtains the electrode for being covered with uniform pomelo peel carbon membrane;
The electrode is subjected to electrochemical copolymerization with polyaniline, polythiophene and polypyrrole respectively using cyclic voltammetry again, obtains pomelo peel
The combination electrode of charcoal and different polymer.
The solid-liquid ratio of the pomelo peel Carbon Materials and nafion solution, dehydrated alcohol is 10mg:4 microlitres: 0.2 milliliter.
When the cyclic voltammetry electro-deposition, the electrolyte used mixes for 0.2mol/L aniline with the sulfuric acid of 0.5mol/L
Liquid.
A kind of pomelo peel carbon and high molecular polymer combination electrode, method as described above are prepared.
A kind of pomelo peel carbon as described above and high molecular polymer combination electrode are applied to supercapacitor.
Compared with the prior art, the present invention has the following beneficial effects:
Although conducting polymer can show very high power density, be equally because it specific capacity it is relatively low and
It is very restricted its application.It attempts with polyaniline, polypyrrole, polythiophene to carry out homemade pomelo peel charcoal respectively herein
It is compound, and Primary Study can be carried out to its electrochemistry.
The present invention provides a kind of easy to operate, easily controllable methods, by homemade pomelo peel charcoal and polyaniline, poly- pyrrole
Cough up, polythiophene carries out compound respectively, and characterization can be carried out to its electrochemistry.It wants to as the flexible development for clicking material
Some thinkings are provided more.
Detailed description of the invention
Fig. 1 is the electro-deposition polyaniline on the glass-carbon electrode for being coated with pomelo peel carbon membrane;
Fig. 2 is the cyclic voltammetric performance of pomelo peel charcoal and polyaniline composite material;
Fig. 3 is the charge-discharge test of pomelo peel charcoal and polyaniline composite material;
Fig. 4 is the cycle performance test of pomelo peel charcoal and polyaniline composite material;
Fig. 5 is the cyclic voltammetric performance of pomelo peel charcoal and Pt/Polypyrrole composite material;
Fig. 6 is the charge-discharge test of pomelo peel charcoal and polyaniline composite material;
Fig. 7 is the cyclic voltammetric performance of pomelo peel charcoal and polythiophene composite material;
Fig. 8 is the charge-discharge test of pomelo peel charcoal and polyaniline composite material.
Specific embodiment
The present invention is described in further detail the claims by following specific embodiments, but does not constitute to this
Any restriction of invention.
Embodiment 1
Pomelo peel charcoal and polyaniline composite material
The electrode of uniform pomelo peel carbon membrane be will be covered with as working electrode, titanium sheet is used as to electrode, mercury/mereurous sulfate electricity
Pole uses the mixed liquor of 0.2mol/L aniline and the 0.5mol/L concentrated sulfuric acid as electrolyte as reference electrode, potential range for-
0.8V-1.4V, sweep speed carries out electro-deposition under conditions of being 0.02V/s, after electro-deposition, is put in drier dry
12h obtains the composite material of pomelo peel charcoal and polyaniline.
Then using obtained combination electrode as working electrode, mercury/Mercurous sulfate electrode is reference electrode, titanium sheet electrode
Be -0.7V-0.1V in potential windows using 0.5mol/L sulfuric acid as electrolyte for electrode, scanning speed be respectively 0.01V/s,
0.02V/s, 0.05V/s carry out cyclic voltammetry;It is -0.7V-0.2V in potential windows, carries out constant current under different current densities
Charge-discharge test;It is 10mV, frequency range 10 in voltage amplitude-2Hz~105Ac impedance measurement is carried out under conditions of Hz, in detail
See Fig. 2-4, in which:
As shown in Figure 2, it is low sweep speed under conditions of, the cyclic voltammetry curve of composite material maintains segment rectangle curve
Feature, similar to the performance of ideal carbon electrode material, especially when sweeping speed is 0.01V/s.
From the figure 3, it may be seen that when the electric current of charge-discharge test increases to 10.0A/g by 2.0A/g, gained charging and discharging curve shape
Shape is still similar to isosceles triangle.Illustrate the composite material in high current charge-discharge, stability is preferable.
As shown in Figure 4, in constant current charge-discharge loop test, in first 100 circulations, with the activity for participating in electrode reaction
Substance and electrolyte contacts are more and more abundant, and specific capacitance has to be increased by a small margin, then tend towards stability.
The beneficial effect of the present embodiment is: preparation is simple, low in cost, by homemade biomass carbon material and conductive polymer
Sub- polymer polyanaline is consistent, and probes into its application in terms of flexible super capacitor;Electrode material can be improved in pomelo peel charcoal
The electric conductivity of material plays certain supporting role to polymer material, and helpful to its overall stability;To a certain degree
Increase the cycle life of electrode active material;
Embodiment 2
Pomelo peel charcoal and Pt/Polypyrrole composite material
The electrode of uniform pomelo peel carbon membrane be will be covered with as working electrode, titanium sheet is used as to electrode, mercury/mereurous sulfate electricity
Use 0.2mol/L p-methyl benzenesulfonic acid and the mixed liquor of 0.1mol/L pyrroles as electrolyte, in potential model as reference electrode in pole
It encloses and arrives 1.4V for -1.4V, rate carries out electro-deposition under conditions of being 0.05V/s, after electro-deposition, is put in drier dry
12h obtains the composite material of pomelo peel charcoal and polypyrrole.
Then using obtained combination electrode as working electrode, mercury/Mercurous sulfate electrode is reference electrode, titanium sheet electrode
Using 0.5mol/L sulfuric acid as electrolyte, to be that -1.2V arrives 1.2V in potential windows, being recycled under different scanning speed to electrode
Volt-ampere test;It is that -1.2V arrives 1.2V in potential windows, carries out constant current charge-discharge test under different current densities;In voltage amplitude
For 10mV, frequency range 10-2Hz~105Ac impedance measurement is carried out under conditions of Hz, is detailed in Fig. 5-6.
Embodiment 3
Pomelo peel charcoal and polythiophene composite material
The electrode of uniform pomelo peel carbon membrane be will be covered with as working electrode, titanium sheet is used as to electrode, saturated calomel electrode
As reference electrode, it is used as electrolyte with the thiophene solution (thiophene monomer is dissolved in boron trifluoride ether solution) of 0.2mol/L.Choosing
With potentiostatic method, setting current potential is 1.3V, sampling time 0.1s, sweep time 1000s.After electro-deposition, it is put in dry
Dry 12h, obtains the composite material of pomelo peel charcoal and polypyrrole in dry device.
It is to electrode, with borontrifluoride with titanium sheet using saturated calomel electrode as reference electrode using glass-carbon electrode as working electrode
Borate ether solution is electrolyte, forms three-electrode system, carries out cyclic voltammetry to polythiophene film.Potential windows be -0.5V~
1.6V is recycled under conditions of scanning speed is 0.01V/s, 0.02V/s, 0.05V/s, 0.07V/s, 0.10V/s respectively
Volt-ampere test, is detailed in Fig. 7-8.
Claims (5)
1. a kind of preparation method of pomelo peel carbon and high molecular polymer combination electrode, which comprises the following steps:
Pomelo peel Carbon Materials are uniformly mixed into obtain slurry with nafion solution, dehydrated alcohol, then slurry are evenly coated in pre-
The glassy carbon electrode surface handled well is placed in drier dry 12h, obtains the electrode for being covered with uniform pomelo peel carbon membrane;Again will
The electrode using cyclic voltammetry respectively with polyaniline, polythiophene and polypyrrole carry out electrochemical copolymerization, obtain pomelo peel charcoal with
The combination electrode of different polymer.
2. the preparation method of pomelo peel carbon and high molecular polymer combination electrode according to claim 1, which is characterized in that institute
The solid-liquid ratio for stating pomelo peel Carbon Materials and nafion solution, dehydrated alcohol is 10mg:4 microlitres: 0.2 milliliter.
3. the preparation method of pomelo peel carbon and high molecular polymer combination electrode according to claim 1, which is characterized in that institute
When stating cyclic voltammetry electro-deposition, the electrolyte used is the sulfuric acid mixture liquid of 0.2mol/L aniline and 0.5mol/L.
4. a kind of pomelo peel carbon and high molecular polymer combination electrode, which is characterized in that by the preparation of claim 1 the method
?.
5. a kind of pomelo peel carbon as claimed in claim 4 and high molecular polymer combination electrode are applied to supercapacitor.
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2019
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