CN109473295A - A method of electrode of super capacitor carbon material is prepared using apple - Google Patents
A method of electrode of super capacitor carbon material is prepared using apple Download PDFInfo
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- CN109473295A CN109473295A CN201710799973.XA CN201710799973A CN109473295A CN 109473295 A CN109473295 A CN 109473295A CN 201710799973 A CN201710799973 A CN 201710799973A CN 109473295 A CN109473295 A CN 109473295A
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- Prior art keywords
- carbon material
- apple
- super capacitor
- inert gas
- carbonization
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
Abstract
The invention discloses a kind of methods for preparing electrode of super capacitor carbon material using apple.Include: the pretreatment of (1) apple: apple surface is cleaned up, stripping and slicing, freeze-drying；(2) the pre- carbonization of apple: the apple of freeze-drying is placed in reactor, is passed through inert gas, is warming up to 300-500 DEG C, 1-3h is reacted, is cooled to room temperature；(3) activation of carbonization carbon material in advance: activator is uniformly mixed with pre- carbonization carbon material, deionized water is added, persistently stirs 8-16h at a temperature of 40-60 DEG C；Reactor is put into remove deionized water completely；It is warming up to 700-900 DEG C under the protection of inert gas, and reacts 1-3h, is then cooled to room temperature the pickling of carbon material after (4) activation under inert gas protection.Present invention process process is simple, low in cost, environmental-friendly, the carbon material excellent electrochemical performance prepared, and specific capacitance is high, good cycling stability, and high rate performance is excellent.
Description
Technical field
The present invention relates to the preparation fields of biomass carbon material, further say, are to be related to a kind of prepare using apple to surpass
The method of grade electrode for capacitors carbon material.
Background technique
Since 21 century, global economy continues to rapidly develop, and people are scientific and technical same with quality of life progress in acquisition
When, the pollution of consumption and environment to earth resource is also increasingly severe.People urgently demand it is more green, it is efficient, can be again
The raw energy and more advanced energy storage and switch technology.Supercapacitor as it is a kind of between traditional capacitor and battery it
Between energy storage device, because its power density height, the charging time is short, has extended cycle life, and operating temperature range is wide and environmental-friendly
Property, cause more and more concerns.According to energy storage mechanism, supercapacitor is broadly divided into two classes.The first kind is double electricity
Layer supercapacitor (EDLCs), it is to form an electric double layer at the interface of electrode material and electrolyte contacts by charge
Energy storage is carried out, this is a physical process.The relatively common electrode material of double electric layers supercapacitor is active carbon.Second
Class is fake capacitance capacitor, its electrode material is usually transition metal oxide or conducting high polymers object, energy are
It is stored by generation in the redox reaction of electrode material surface Rapid reversible, this is a chemical process.Phase
Than in double layer capacitor, the specific capacitance and energy density of fake capacitance capacitor are higher, but power density and cyclical stability
It is poor.Therefore, the advantages of both supercapacitors is joined together is a current hot issue.
So far, it as matrix and is adulterated with hydrogen reduction using carbon materials such as graphene oxide, carbon fiber, carbon nanotubes
The material of the dispersion of property has been widely used in supercapacitor, they possess high-specific surface area, good flexible
Property, outstanding mechanical performance etc., and show outstanding energy storage performance.However, they there is also some disadvantages, examples
Such as, the stacking rendezvous problem of graphene oxide, it is at high cost, prepare many and diverse etc., these are all limited its application.
Summary of the invention
To solve the problem in the prior art, super capacitor is prepared using apple the object of the present invention is to provide a kind of
The method of device electrode carbon material.The technical process is simple, low in cost, environmental-friendly, the carbon material chemical property prepared
Excellent, specific capacitance is high, good cycling stability, and high rate performance is excellent.
The object of the present invention is to provide a kind of methods for preparing electrode of super capacitor carbon material using apple.
Include:
(1) pretreatment of apple: apple surface being cleaned up, stripping and slicing, freeze-drying；
(2) the pre- carbonization of apple: being placed in reactor for the apple of freeze-drying, be passed through inert gas, be warming up to 300-500 DEG C,
1-3h is reacted, then cooled to room temperature under inert gas protection；
(3) activation of carbonization carbon material in advance: activator is uniformly mixed with the pre- carbonization carbon material that step (2) obtains, is added
Enter deionized water, persistently stirs 8-16h at a temperature of 40-70 DEG C；Reactor is put into remove deionized water completely；In indifferent gas
It is warming up to 700-900 DEG C under the protection of body, and reacts 1-3h, is then cooled to room temperature under inert gas protection；
(4) pickling of carbon material after activating: acid solution to solution is added into the carbon material after activation and is shown as neutral, thoroughly
Analysis, then removes moisture removal.
Wherein, preferably:
The inert gas is one kind or mixing of nitrogen, helium or argon gas.
The acid solution is hydrochloric acid solution, sulfuric acid solution or nitric acid solution.
In step (2) and step (3), heating rate is with 5-10 DEG C/min.
The mass ratio of pre- carbonization carbon material and activator that step (2) obtains is 1:2.5~4.5.
In step (3), the dosage of deionized water is 10-20 times of activator quality.
The activator is potassium hydroxide, sodium hydroxide, and potassium carbonate is one or more of in sodium carbonate.
Following technical scheme specifically can be used in the present invention:
(1) pretreatment of apple: apple surface being cleaned up, stripping and slicing, freeze-drying；
(2) the pre- carbonization of apple: the apple of freeze-drying is placed in reactor, inert gas is passed through, with the speed liter of 5 DEG C/min
Temperature reacts 1-3h to 300-500 DEG C, then natural cooling under inert gas protection；
(3) activation of carbonization carbon material in advance: activator is mixed in proportion with the pre- carbonization carbon material that step (2) obtains
Even, the mass ratio of carbon material and activator is 1:2.5~4.5；A certain amount of deionized water is added, persistently stirs at a certain temperature
12h；Reactor is put into remove deionized water completely；It is warming up to 700-900 DEG C under the protection of inert gas, and reacts 1-
3h, then natural cooling under inert gas protection；
(4) pickling of carbon material after activating: a certain amount of acid solution to solution is added into the carbon material after activation and shows
For neutrality, mixed liquor is poured into bag filter and is sealed, bag filter is then immersed into deionized water；Carbon material after dialysis is put into
It is in reactor that moisture removal is clean.
The carbon source of electrode of super capacitor carbon material prepared by the present invention is apple, and abundant raw material is easy to get, preparation method letter
Single, low manufacture cost can be prepared on a large scale, and raw material used in preparation process is to human body and environmentally friendly, clean and environmental protection, green
It is sustainable.
Hetero atom auto-dope electrode of super capacitor carbon material content of heteroatoms prepared by the present invention can achieve 15%, than
Surface area can achieve 1600m2/ g, and the specific capacitance of the electrode material for super capacitor of its production can achieve 325F/g.
Detailed description of the invention
Fig. 1 is to be prepared in embodiment 1 using apple as the BET adsorption curve of the electrode of super capacitor carbon material of carbon source；
Fig. 2 is to be prepared in embodiment 1 using apple as the cyclic voltammetric of the electrode of super capacitor carbon material electrode of carbon source
Test curve；
Fig. 3 is filling by the constant current of the electrode of super capacitor carbon material electrode of carbon source of apple of preparing in embodiment 1
Discharge lines；
Fig. 4 is to be prepared in embodiment 1 using apple as the high rate performance of the electrode of super capacitor carbon material electrode of carbon source
Curve.
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated.
Embodiment 1:
(1) pretreatment of apple: apple surface being cleaned up, stripping and slicing, freeze-drying；
(2) the pre- carbonization of apple: the apple of freeze-drying is placed in reactor, inert nitrogen gas is passed through, with the speed of 5 DEG C/min
Degree is warming up to 300 DEG C, and reacts 1h, then natural cooling under inert gas protection；
(3) activation of carbonization carbon material in advance: the activator KOH pre- carbonization carbon material obtained with step (2) is mixed in proportion
It closes uniformly, the mass ratio of carbon material and KOH are 1:3.5；The ionized water of 15 times of activator quality is added, in 40 DEG C of lasting stirrings
16h；Reactor is put into remove deionized water completely；It is warming up to 700 DEG C under the protection of inert gas argon gas, and reacts 1h,
Subsequent cooled to room temperature under inert gas protection；
(4) it is aobvious to solution that a certain amount of hydrochloric acid solution the pickling of carbon material after activating: is added into the carbon material after activation
It is shown as neutral, mixed liquor is poured into bag filter and is sealed, bag filter is then immersed into deionized water；Carbon material after dialysis is put
Enter in reactor that moisture removal is clean.
Embodiment 2:
(1) pretreatment of apple: apple surface being cleaned up, stripping and slicing, freeze-drying；
(2) the pre- carbonization of apple: the apple of freeze-drying is placed in reactor, inert gas argon gas is passed through, with 10 DEG C/min's
Speed is warming up to 500 DEG C, and reacts 2h, then cooled to room temperature under inert gas protection；
(3) activation of carbonization carbon material in advance: the activator NaOH pre- carbonization carbon material obtained with step (2) is mixed in proportion
It closes uniformly, the mass ratio of carbon material and NaOH are 1:2.5；The ionized water of 20 times of activator quality is added, in 50 DEG C of lasting stirrings
12h；Reactor is put into remove deionized water completely；It is warming up to 800 DEG C under the protection of inert nitrogen gas, and reacts 2h,
Subsequent cooled to room temperature under inert gas protection；
(4) it is aobvious to solution that a certain amount of hydrochloric acid solution the pickling of carbon material after activating: is added into the carbon material after activation
It is shown as neutral, mixed liquor is poured into bag filter and is sealed, bag filter is then immersed into deionized water；Carbon material after dialysis is put
Enter in reactor that moisture removal is clean.
Embodiment 3
(1) pretreatment of apple: apple surface being cleaned up, stripping and slicing, freeze-drying；
(2) the pre- carbonization of apple: the apple of freeze-drying is placed in reactor, inert nitrogen gas is passed through, with 10 DEG C/min's
Speed is warming up to 500 DEG C, and reacts 3h, then natural cooling under inert gas protection；
(3) activation of carbonization carbon material in advance: the pre- carbonization carbon material that activator potassium carbonate and step (2) are obtained is in proportion
It is uniformly mixed, the mass ratio of carbon material and potassium carbonate is 1:4.5；The deionized water of 10 times of activator quality is added, in 60 DEG C of temperature
8h is persistently stirred under degree；Reactor is put into remove deionized water completely；It is warming up to 900 DEG C under the protection of inert gas, and
3h is reacted, then cooled to room temperature under inert gas protection；
(4) a certain amount of sulfuric acid solution liquid the pickling of carbon material after activating: is added into the carbon material after activation to solution
It is shown as neutral, mixed liquor is poured into bag filter and is sealed, bag filter is then immersed into deionized water；By the carbon material after dialysis
It is put into reactor that moisture removal is clean.
Effect of the invention is verified by following tests:
Test
Select platinized platinum be used as matrix, Example 3 preparation using apple as the carbon material of carbon source, polyvinylidene fluoride quality
Than being tuned into paste, being applied on platinized platinum, be subsequently placed at 120 DEG C of drying 6h of air dry oven for 9:1.As working electrode.
Cyclic voltammetry is carried out using three-electrode system and constant current charge-discharge is tested, silver chloride electrode is reference electrode,
Blank platinized platinum is to electrode, and the electrode of preparation is working electrode, in 1M H2SO4It is tested in solution, voltage range is -0.1
~0.9V.
Test result:
(1) reach 1600m by the specific surface area of the electrode of super capacitor carbon material of carbon source of apple obtained by2/ g,
Content of heteroatoms reaches 15%；
(2) aobvious by the cyclic voltammetry curve of the electrode of super capacitor carbon material electrode of carbon source of apple prepared by
The redox peaks generated by hetero atom auto-dope are shown；
(3) being shown by the constant current charge-discharge line of the electrode of super capacitor carbon material electrode of carbon source of apple prepared by
Its characteristic for having double layer capacitor；
(4) being shown by the high rate performance curve of the electrode of super capacitor carbon material electrode of carbon source of apple prepared by
Its specific capacitance can achieve 325F/g and possess good high rate performance.
Claims (7)
1. a kind of method for preparing electrode of super capacitor carbon material using apple, it is characterised in that the described method includes:
(1) pretreatment of apple: apple surface being cleaned up, stripping and slicing, freeze-drying；
(2) the pre- carbonization of apple: being placed in reactor for the apple of freeze-drying, be passed through inert gas, is warming up to 300-500 DEG C, reaction
1-3h, then cooled to room temperature under inert gas protection；
(3) activation of carbonization carbon material in advance: activator is uniformly mixed with the pre- carbonization carbon material that step (2) obtains, addition is gone
Ionized water persistently stirs 8-16h at a temperature of 40-60 DEG C；Reactor is put into remove deionized water completely；In inert gas
It is warming up to 700-900 DEG C under protection, and reacts 1-3h, is then cooled to room temperature under inert gas protection；
(4) pickling of carbon material after activating: acid solution to solution being added into the carbon material after activation and is shown as neutral, dialysis,
Then moisture removal is removed.
2. the method for preparing electrode of super capacitor carbon material using apple as described in claim 1, it is characterised in that:
The inert gas is one kind or mixing of nitrogen, helium or argon gas.
3. the method for preparing electrode of super capacitor carbon material using apple as described in claim 1, it is characterised in that:
The acid solution is hydrochloric acid solution, sulfuric acid solution or nitric acid solution.
4. the method for preparing electrode of super capacitor carbon material using apple as described in claim 1, it is characterised in that:
In step (2) and step (3), heating rate is with 5-10 DEG C/min.
5. the method for preparing electrode of super capacitor carbon material using apple as described in claim 1, it is characterised in that
The mass ratio of pre- carbonization carbon material and activator that step (2) obtains is 1:2.5~4.5.
6. the method for preparing electrode of super capacitor carbon material using apple as described in claim 1, it is characterised in that:
In step (3), the dosage of deionized water is 10-20 times of activator quality.
7. the method for preparing electrode of super capacitor carbon material using apple as claimed in claim 6, it is characterised in that:
The activator is potassium hydroxide, sodium hydroxide, and potassium carbonate is one or more of in sodium carbonate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710799973.XA CN109473295A (en) | 2017-09-07 | 2017-09-07 | A method of electrode of super capacitor carbon material is prepared using apple |
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| CN201710799973.XA CN109473295A (en) | 2017-09-07 | 2017-09-07 | A method of electrode of super capacitor carbon material is prepared using apple |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110282625A (en) * | 2019-07-31 | 2019-09-27 | 上海应用技术大学 | A kind of preparation method and application of electrode material for super capacitor |
| CN110668421A (en) * | 2019-10-29 | 2020-01-10 | 江苏科技大学 | Preparation method of biomass porous carbon material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2259920A1 (en) * | 2005-04-01 | 2006-10-16 | Consejo Superior Investig. Cientificas | Method of producing activated carbons from apple pulp for use as electrodes in electric double-layer capacitors (edlc) |
| CN105140052A (en) * | 2015-10-13 | 2015-12-09 | 东南大学 | Super-capacitor carbon electrode material preparation method based on taxodiaceae plant cones |
| CN105914372A (en) * | 2016-06-24 | 2016-08-31 | 陕西科技大学 | Three-dimensional porous biomass carbon nanomaterial prepared from pomace, and preparation method and application therefor |
| CN106927463A (en) * | 2017-03-30 | 2017-07-07 | 黑龙江大学 | A kind of method for preparing electrode of super capacitor carbon material as carbon source with radish |
-
2017
- 2017-09-07 CN CN201710799973.XA patent/CN109473295A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2259920A1 (en) * | 2005-04-01 | 2006-10-16 | Consejo Superior Investig. Cientificas | Method of producing activated carbons from apple pulp for use as electrodes in electric double-layer capacitors (edlc) |
| CN105140052A (en) * | 2015-10-13 | 2015-12-09 | 东南大学 | Super-capacitor carbon electrode material preparation method based on taxodiaceae plant cones |
| CN105914372A (en) * | 2016-06-24 | 2016-08-31 | 陕西科技大学 | Three-dimensional porous biomass carbon nanomaterial prepared from pomace, and preparation method and application therefor |
| CN106927463A (en) * | 2017-03-30 | 2017-07-07 | 黑龙江大学 | A kind of method for preparing electrode of super capacitor carbon material as carbon source with radish |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110282625A (en) * | 2019-07-31 | 2019-09-27 | 上海应用技术大学 | A kind of preparation method and application of electrode material for super capacitor |
| CN110668421A (en) * | 2019-10-29 | 2020-01-10 | 江苏科技大学 | Preparation method of biomass porous carbon material |
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Application publication date: 20190315 |