CN110136992A - A method of electrode material for super capacitor is prepared using grape - Google Patents
A method of electrode material for super capacitor is prepared using grape Download PDFInfo
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- CN110136992A CN110136992A CN201910438558.0A CN201910438558A CN110136992A CN 110136992 A CN110136992 A CN 110136992A CN 201910438558 A CN201910438558 A CN 201910438558A CN 110136992 A CN110136992 A CN 110136992A
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- grape
- electrode material
- super capacitor
- based biomass
- preparing electrode
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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
- H01G11/24—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
- H01G11/22—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
- H01G11/84—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 material for super capacitor using grape, using grape as carbon materials material precursor, by adding different modifying agent, in such a way that low temperature is carbonized in advance and high temperature cabonization activation combines, quickly prepare the electrode material with three-dimensional multistage pore structure and class graphene-structured, and by tridimensional network and class graphene-structured, enhances its cycle performance, realize different capacitor specific capacities.For the present invention using biomass grape common in living as raw material, abundance is cheap; preparation method has easy to operate, repeatable strong; no pollution to the environment meets the demand of sustainable development and environmental protection, can effectively reduce the cost for preparing electrode material；The biomass grape base electrode material of preparation, specific capacitance with higher and good cyclical stability are a kind of ideal electrode material for super capacitor, have vast potential for future development.
Description
Technical field
The present invention relates to a kind of methods of electrode material for super capacitor, and in particular to a kind of to prepare super electricity using grape
The method of container electrode material belongs to electrochemistry and novel energy resource material technology field.
Background technique
In recent years, with economic rapid development, the problem of energy shortages, becomes increasingly conspicuous, and high-performance energy storage device is to development
Eco-friendly renewable energy is of great significance.
Supercapacitor is a kind of novel energy storage device, because it is fast with charge/discharge speed, energy density is high, ratio
Power is high, the advantages that having extended cycle life, and can be widely applied to energy storage device.Supercapacitor is divided into electric double layer type super capacitor
Device and fake capacitance type supercapacitor, electric double layer type supercapacitor are based on electrostatic charge in inert electrode diffusion into the surface and accumulation
The electric double layer of formation, and fake capacitance type supercapacitor is then that reversible faraday's reaction occurs based on surface of active material.
Currently, various carbon materials can be used for electrode of super capacitor, wherein mainly including porous carbon, graphene, active carbon
With carbon nanotube etc..Porous carbon has bigger serface, adjustable pore structure, low cost and stable chemical characteristic etc. excellent
Point is the necessary condition that can become electrode material for super capacitor.Wherein porous carbon electrodes store energy, layer by electric double layer
Shape class graphene-structured equally can quickly store charge, and therefore, the carbon material of bigger serface and ion fast transferring is
The necessary structure of high-efficiency energy-storage.
The preparation of electrode material for super capacitor is to mix the carbon material containing active material and conductive agent and binder etc.
Sauce is made in conjunction, then smears compression moulding；But commercialization active charcoal preparing process cost is excessively high at present, and product pattern is general
Mostly three-dimensional structure, can not be fully controllable.
Summary of the invention
To solve the deficiencies in the prior art, the purpose of the present invention is to provide a kind of quickly prepared using grape to have three-dimensional
The preparation method of the electrode material of the supercapacitor of hierarchical porous structure or class graphene-structured.
In order to achieve the above objectives, the present invention adopts the following technical scheme that:
A method of electrode material for super capacitor is prepared using grape, comprising the following steps:
S1, it after cleaning up grape, dries；
S2, by after drying grape and activator be mixed in a certain ratio uniformly after, be placed in Muffle furnace and be carbonized in advance, make
Obtain grape based biomass carbon；
S3, it after grape based biomass carbon is clayed into power, is sieved, grape based biomass carbon dust is made；
S4, take nitrogen as protection gas, grape based biomass carbon dust is placed on carbonization-activation in tube furnace, after cooling,
Grape based biomass carbon material is made.
S5, grape based biomass carbon material is washed to neutrality, after dry, electrode material for super capacitor is made.
Grape based biomass carbon material in above-mentioned steps S4 has three-dimensional multistage pore structure and class graphene-structured.
Cleaning solution in above-mentioned steps S1 includes ethyl alcohol and deionized water, and drying temperature is 80-105 DEG C, and drying time is
12-24h。
Pre- carbonization in above-mentioned steps S2 carbonizes 1-3h to be warming up to 150-300 DEG C with the heating rate of 2-5 DEG C/min；
Preferably, pre- carburizing temperature is 300 DEG C.
Sieve in above-mentioned steps S3 is 50-400 mesh.
Carbonization-activation in above-mentioned steps S4, to be warming up to 600-1000 DEG C with the heating rate of 2-10 DEG C/min, carbonization
Activate 1-4h；Preferably, carbonization-activation temperature is 700-900 DEG C.
Cleaning solution in above-mentioned steps S5 is deionized water, and dry environment is vacuum, and drying temperature is 60 DEG C, drying time
For 12-24h.
The mass ratio that grape and activator are pressed in above-mentioned steps S2 is 1:1-1:5, it is preferred that mass ratio 1:2.
Activator in above-mentioned steps S2 includes acidic active agent, bases activator；Acidic active agent includes H2SO4、
H3PO4、HCl、HNO3、AlCl3、NH4Cl、ZnCl2；Bases activator includes NaOH, KOH, Ca (OH)2。
The invention has the beneficial effects that:
A kind of method preparing electrode material for super capacitor using grape of the invention, using grape as carbon material forerunner
Body, by adding different modifying agent, in such a way that low temperature is carbonized in advance and high temperature cabonization activation combines, quickly preparation is provided
There is the electrode material of three-dimensional multistage pore structure or class graphene-structured, and passes through tridimensional network, class graphene-structured, enhancing
Its cycle performance realizes different capacitor specific capacities.
The present invention is using biomass grape common in living as raw material, and abundance is cheap, and preparation method has
Easy to operate, repeatable strong, no pollution to the environment meets the demand of sustainable development and environmental protection, can effectively reduce system
The cost of standby electrode material；The biomass grape base electrode material of preparation, specific capacitance with higher and good stable circulation
Property, it is a kind of ideal electrode material for super capacitor, there is vast potential for future development.
Detailed description of the invention
Fig. 1 is transmission electron microscope (TEM) photo (figure a of electrode material for super capacitor prepared by the embodiment of the present invention 1,2
It is H for KOH-800, figure b3PO4-800)。
Fig. 2 is N2 absorption and the pore size distribution curve of electrode material for super capacitor prepared by the embodiment of the present invention 1,2
Figure.
Fig. 3 be the embodiment of the present invention 1,2 prepare electrode material for super capacitor cyclic voltammetry curve figure (figure a be
KOH-800, figure b are H3PO4-800)。
Fig. 4 is that (figure a is KOH- to the impedance plot of electrode material for super capacitor for preparing of the embodiment of the present invention 1,2
800, figure b are H3PO4-800)。
Specific embodiment
Specific introduce is made to the present invention below in conjunction with the drawings and specific embodiments.
Reagent and instrument used in the present invention, see the table below 1 and 2:
1 main agents of table
2 key instrument of table
Embodiment 1
A method of electrode material for super capacitor is prepared using grape, comprising the following steps:
S1, after cleaning grape with ethyl alcohol and deionized water respectively, 12h is dried at 95 DEG C；
S2, the grape after drying is mixed with KOH by the mass ratio of 1:2, adds 100mL deionized water, the magnetic at 25 DEG C
Power stirs 3h, and solution after mixing, is placed in crucible, and is placed in Muffle furnace and is carbonized in advance, with the heating rate of 5 DEG C/min
200 DEG C are warming up to, then is warming up to 300 DEG C with the heating rate of 2 DEG C/min, 1h is carbonized, grape based biomass carbon is made；
S3, after grape based biomass carbon is clayed into power, it is sieved through sieve with the stainless steel of 400 mesh, grape based biomass is made
Carbon dust；
S4, grape based biomass carbon dust in 3 is placed in tube furnace, N2To protect gas, with the heating speed of 5 DEG C/min
Rate heats up 400 DEG C, keeps the temperature 1h,；It is heated up 800 DEG C with the heating rate of 2 DEG C/min again, carbonization-activation 2h；Portugal is made in natural cooling
Grape based biomass carbon material.
S5, grape based biomass carbon material deionized water suction filtration is washed till neutrality, after 60 DEG C of vacuum drying, is made super
Grade capacitor electrode material, is labeled as KOH-800.
Embodiment 2
A method of electrode material for super capacitor is prepared using grape, comprising the following steps:
S1, after cleaning grape with ethyl alcohol and deionized water respectively, 12h is dried at 95 DEG C；
S2, by the grape and H after drying3PO4By 8g:40mL, 100mL deionized water, the magnetic agitation at 25 DEG C are added
3h, solution after mixing, is placed in crucible, and is placed in Muffle furnace and is carbonized in advance, is warming up to the heating rate of 5 DEG C/min
200 DEG C, then 300 DEG C are warming up to the heating rate of 2 DEG C/min, 1h is carbonized, grape based biomass carbon is made；
S3, after grape based biomass carbon is clayed into power, it is sieved through sieve with the stainless steel of 400 mesh, grape based biomass is made
Carbon dust；
S4, grape based biomass carbon dust in 3 is placed in tube furnace, N2To protect gas, with the heating speed of 5 DEG C/min
Rate heats up 400 DEG C, keeps the temperature 1h,；It is heated up 800 DEG C with the heating rate of 2 DEG C/min again, carbonization-activation 2h；Portugal is made in natural cooling
Grape based biomass carbon material.
S5, grape based biomass carbon material deionized water suction filtration is washed till neutrality, after 60 DEG C of vacuum drying, is made super
Grade capacitor electrode material, is labeled as H3PO4-800.
As shown in Figure 1, transmission electron microscope (TEM) photo of the electrode material for super capacitor prepared for embodiment 1,2；It can
See, scheme the KOH-800 prepared at 800 DEG C in a, there is three-dimensional multistage pore structure (a), prepared at 800 DEG C in figure b
H3PO4- 800, there is class graphene-structured.
As shown in Fig. 2, N2 absorption and pore size distribution curve for the electrode material for super capacitor of the preparation of embodiment 1,2
Figure；As it can be seen that KOH-800, H for being prepared at 800 DEG C3PO4- 800, three-dimensional hierarchical porous structure and class graphene-structured all have
Higher specific surface area and biggish pore volume.
As shown in figure 3, be embodiment 1,2 prepare electrode material for super capacitor cyclic voltammetry curve figure (figure a be
KOH-800, figure b are H3PO4-800)；As it can be seen that KOH-800, H for being prepared at 800 DEG C3PO4- 800, three-dimensional hierarchical porous structure
With class graphene-structured, under different current densities, especially at 10A/g, specific capacity all with higher.
As shown in figure 4, being that (figure a is KOH- to the impedance plot of electrode material for super capacitor for preparing of embodiment 1,2
800, figure b are H3PO4-800)；As it can be seen that KOH-800, H for being prepared at 800 DEG C3PO4- 800, three-dimensional hierarchical porous structure and class
Graphene-structured all has smaller impedance, and after 1000 circulations, since wellability increase makes impedance further increase reduction,
Show that it is all with good performance.
Confirm biomass grape base carbon material specific capacitance with higher (80-100F/g) and good stable circulation
Property, after cycle charge-discharge 1000 times, specific capacitance stills remain in (76.3-97.6F/g), sufficiently proves prepared by the present invention
Grape base carbon material can preferably be applied to electrode material for super capacitor.
The basic principles, main features and advantages of the invention have been shown and described above.The technical staff of the industry should
Understand, the above embodiments do not limit the invention in any form, all obtained by the way of equivalent substitution or equivalent transformation
Technical solution is fallen within the scope of protection of the present invention.
Claims (9)
1. a kind of method for preparing electrode material for super capacitor using grape, which comprises the following steps:
S1, it after cleaning up grape, dries；
S2, by after drying grape and activator be mixed in a certain ratio uniformly after, be placed in Muffle furnace and be carbonized in advance, be made Portugal
Grape based biomass carbon；
S3, it after grape based biomass carbon is clayed into power, is sieved, grape based biomass carbon dust is made；
S4, take nitrogen as protection gas, grape based biomass carbon dust is placed on carbonization-activation in tube furnace, after cooling, is made
Grape based biomass carbon material.
S5, grape based biomass carbon material is washed to neutrality, after dry, electrode material for super capacitor is made.
2. a kind of method for preparing electrode material for super capacitor using grape according to claim 1, which is characterized in that
Grape based biomass carbon material in the step S4 has three-dimensional multistage pore structure and class graphene-structured.
3. a kind of method for preparing electrode material for super capacitor using grape according to claim 1, which is characterized in that
Cleaning solution in the step S1 includes ethyl alcohol and deionized water, and drying temperature is 80-105 DEG C, drying time 12-24h.
4. a kind of method for preparing electrode material for super capacitor using grape according to claim 1, which is characterized in that
Pre- carbonization in the step S2 carbonizes 1-3h to be warming up to 150-300 DEG C with the heating rate of 2-5 DEG C/min.
5. a kind of method for preparing electrode material for super capacitor using grape according to claim 1, which is characterized in that
Sieve in the step S3 is 50-400 mesh.
6. a kind of method for preparing electrode material for super capacitor using grape according to claim 1, which is characterized in that
Carbonization-activation in the step S4, to be warming up to 600-1000 DEG C with the heating rate of 2-10 DEG C/min, carbonization-activation 1-4h.
7. a kind of method for preparing electrode material for super capacitor using grape according to claim 1, which is characterized in that
Cleaning solution in the step S5 is deionized water, and dry environment is vacuum, and drying temperature is 60 DEG C, drying time 12-
24h。
8. a kind of method for preparing electrode material for super capacitor using grape according to claim 1, which is characterized in that
The mass ratio that grape and activator are pressed in the step S2 is 1:1-1:5.
9. a kind of method for preparing electrode material for super capacitor using grape according to claim 1, which is characterized in that
Activator in the step S2 includes acidic active agent, bases activator；
The acidic active agent includes H2SO4、H3PO4、HCl、HNO3、AlCl3、NH4Cl、ZnCl2；
The bases activator includes NaOH, KOH, Ca (OH)2。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111333068A (en) * | 2020-02-28 | 2020-06-26 | 西南大学 | Preparation method and application of biomass porous carbon material based on nut shells |
| CN111689485A (en) * | 2020-05-29 | 2020-09-22 | 上海应用技术大学 | Method for preparing carbon material by low-temperature carbonization of biomass |
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| CN104843685A (en) * | 2015-04-10 | 2015-08-19 | 四川大学 | Method for preparation of three-dimensional porous graphene carbon electrode material from livestock excrement |
| CN106587055A (en) * | 2016-11-17 | 2017-04-26 | 华南理工大学 | Biomass-based porous carbon material, preparation method thereof, and application thereof in supercapacitor |
| CN107601501A (en) * | 2017-10-23 | 2018-01-19 | 桂林理工大学 | A kind of preparation method and applications of biomass-based porous carbon |
| CN109081342A (en) * | 2018-08-03 | 2018-12-25 | 成都城电电力工程设计有限公司 | A kind of biomass porous active carbon of nipa palm leaf and its preparation method and application |
-
2019
- 2019-05-24 CN CN201910438558.0A patent/CN110136992A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104843685A (en) * | 2015-04-10 | 2015-08-19 | 四川大学 | Method for preparation of three-dimensional porous graphene carbon electrode material from livestock excrement |
| CN106587055A (en) * | 2016-11-17 | 2017-04-26 | 华南理工大学 | Biomass-based porous carbon material, preparation method thereof, and application thereof in supercapacitor |
| CN107601501A (en) * | 2017-10-23 | 2018-01-19 | 桂林理工大学 | A kind of preparation method and applications of biomass-based porous carbon |
| CN109081342A (en) * | 2018-08-03 | 2018-12-25 | 成都城电电力工程设计有限公司 | A kind of biomass porous active carbon of nipa palm leaf and its preparation method and application |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111333068A (en) * | 2020-02-28 | 2020-06-26 | 西南大学 | Preparation method and application of biomass porous carbon material based on nut shells |
| CN111689485A (en) * | 2020-05-29 | 2020-09-22 | 上海应用技术大学 | Method for preparing carbon material by low-temperature carbonization of biomass |
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