CN106587059A - Activated carbon modification method for electrochemical energy storage devices - Google Patents
Activated carbon modification method for electrochemical energy storage devices Download PDFInfo
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- CN106587059A CN106587059A CN201611133261.6A CN201611133261A CN106587059A CN 106587059 A CN106587059 A CN 106587059A CN 201611133261 A CN201611133261 A CN 201611133261A CN 106587059 A CN106587059 A CN 106587059A
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- activated carbon
- electrochemical energy
- storing device
- energy storing
- ammonium salt
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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
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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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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
Abstract
The invention proposes an activated carbon modification method for electrochemical energy storage devices, which comprises the following steps: after being mixed, activated carbon powder and nitrogenous activation solution are put into a pressure-resistant reaction kettle and activated under 80 DEG C to 150 DEG C, and after filtration and drying, a modified activated carbon material for high-performance electrochemical energy storage devices is obtained. The invention is simple and convenient in process, no pollution is produced, and the prepared product has a large specific surface area and excellent electrochemical properties.
Description
Technical field
The present invention relates to a kind of modifying method of activated carbon for electrochemical energy storing device, in belonging to electrochemical energy storing device
Electrode material field.
Technical background
The features such as electrochemical energy storing device has big life-span length, power, environmental protection and is easy to carry, as electronic equipment
It is with a wide range of applications with the power supply of automobile.Battery and ultracapacitor as important electrochemical energy storing device mainly by
Electrode, electrolyte, barrier film, end plate, lead and encapsulation are constituted, and its chemical property is mainly determined by the performance of electrode material, its
Middle active carbon material is one of the most frequently used negative material.
The hydrophobic macromolecules that active carbon material is made up of numerous not localization carbon atoms, are unfavorable for disperseing in a solvent,
Which limits the good characteristic as electrode material that the material itself has.Additionally, because of raw material and preparation technology not
Together, cause commercial active carbon material spread in performance uneven.Therefore, activated carbon is modified, i.e., introduces new in activated carbon surface
Hydrophilic nitrogenous, oxygen functional group, the wellability that can not only improve carbon can also impart to its extra physical chemistry function,
Improve their practical application performances.
The current method that process is modified to activated carbon, mainly has（1）Heating, the Cryogenic air in 300～350 DEG C
In aoxidized or in 800～1000 DEG C of high temperature inert atmosphere dispose；(2) plasma processing method；（3）Microwave method；（4）Add
Plus activator, activator mainly has concentrated nitric acid, strong aqua ammonia, carbamide, tripolycyanamide etc..There is apparatus expensive, energy consumption in above method
It is high, have certain environment to pollute or performance improves the various problems such as unobvious, limit its application industrially.Therefore, overcome existing
There is the deficiency of technology, develop a kind of method of modifying of the activated carbon for electrochemical energy storing device and there is important effect.
The content of the invention
The present invention provides a kind of modifying method of activated carbon for electrochemical energy storing device, is raw material Jing by active carbon powder
Nitrogen-containing functional group is modified, and the product prepared has big specific surface area and excellent chemical property, is suitable to electrochemistry storage
The electrode material of energy device is used.
The technical solution used in the present invention is：A kind of method of modifying of the activated carbon for electrochemical energy storing device, including
Following steps：
（1）Prepare nitrogenous activating solution：Inorganic ammonium salt is added to filling in the container that mass percent concentration is 15～25% ammonia simultaneously
Stirring, treats that solid is completely dissolved；Wherein ammonia and the mass ratio of ammonium salt are 1:（0.05～0.2）；Note the addition of ammonium salt
Amount can not be more than its dissolubility when temperature is configured；
（2）By activated carbon raw material powder and step（1）The volume of nitrogenous activating solution is by 1 kg:（3～8）The ratio mix homogeneously of L,
Subsequently mixture is placed in 10～20 minutes in the vacuum tank that vacuum is -0.1MPa；
（3）By step（2）Activated carbon mixed liquor be transferred in pressure reactor, activated at 80～150 DEG C, during insulation
Between 2～4 hours, be subsequently cooled to room temperature；
（4）By step（3）Gained mixed liquor after filtering, is dried to filter cake, obtains final product the work for electrochemical energy storing device
Property charcoal.
In above-mentioned technical proposal, step（4）The filtrate for obtaining, can Reusability Jing after concentration allotment.
In above-mentioned technical proposal, the inorganic ammonium salt is activator promotor, preferential ammonium sulfate or ammonium chloride.
Beneficial effect：Compared with prior art, it is an advantage of the current invention that：
（1）The present invention can be greatly reduced the consumption of ammonia and improve the nitrogen in solution and be contained using inorganic ammonium salt as activator promotor
Amount, and then mitigate corrosion and problem of environmental pollution of the alkali to equipment in subsequent activation process；Lived using vacuum impregnation containing nitrogen solution
Property charcoal, improve the uniformity of activating solution and active particle exposure level and distribution, accelerate diffusion of the solution in activated carbon and inhale
Attached process；3rd, soak activated carbon mixed solution be separated by filtration after, filtrate can multiple Reusability；
（2）The present invention strengthens activation modification process using nitrogenous activating solution-hydro-thermal combination method, improves production technology, saves energy
Consumption, reduces pollution, and the active carbon material pore structure development that specific area is obtained is more ripe, for electrochemical energy storing device
Chemical property is good during electrode material.
In sum, the present invention is lived with activated carbon as raw material by activating solution vacuum impregnation, nitrogenous activating solution-hydro-thermal method
Change modified technology, the nitrogenous absorbent charcoal material prepared has big specific surface area and excellent chemical property, in electrification
Learn energy storage device field and there is wide application prospect.
Description of the drawings
The scanning electron microscope of modified activated carbon (b) prepared by Fig. 1 activated carbon raw materials (a) and the embodiment of the present invention 3 is to contrasting
Piece；
Fig. 2 activated carbon raw materials (a), activated carbon changing of preparing of Jing ammonia activation modification (b) and the embodiment of the present invention 3 at room temperature
The infrared spectrum comparison diagram of property activated carbon (c)；
Fig. 3 is the cyclic voltammetry curve of activated carbon electrodes prepared by the embodiment of the present invention 1；
Fig. 4 is activated carbon prepared by the embodiment of the present invention 2（b）With activated carbon raw material（a）Electrochemical AC impedance comparison diagram.
Specific embodiment
The following examples will be further described to the present invention, but not thereby limiting the invention.
In following examples, the ammonia concn being related to refers to mass percent concentration.
Embodiment 1
The ratio of configuration quality is 1（15% ammonia）∶0.2（Activator promotor ammonium sulfate）Activating solution, stirring, treat that solid is completely dissolved
；With commercially available activated carbon as raw material, by quality（kg）After being uniformly mixed for 1: 4 with the ratio of the volume (L) of activating solution,
It is placed in 10 minutes in the vacuum tank that vacuum is -0.1MPa, subsequently mixture is transferred in high pressure resistant reactor, in 100 DEG C
It is incubated 120 min；Most at last activation products are filtered, and filter cake is dried 2h at 100 DEG C.
Embodiment 2
The ratio of the amount of configuration material is 1（20% ammonia）∶0.15（Activator promotor ammonium sulfate）Activating solution, stirring, treat that solid is complete
Dissolving；By commercially available activated carbon raw material, by quality（kg）It is uniformly mixed for 1: 4 with the ratio of the volume (L) of activating solution
Afterwards, it is placed in 15 minutes in the vacuum tank that vacuum is -0.1MPa, subsequently mixture is transferred in high pressure resistant reactor, in 80
DEG C insulation 180 min；Most at last activation products are filtered, and filter cake is dried 2h at 100 DEG C.
Embodiment 3
The ratio of the amount of configuration material is 1（25% ammonia）∶0.1（Activator promotor ammonium sulfate）Activating solution, stirring, treat that solid is complete
Dissolving；By commercially available activated carbon raw material, by quality（kg）It is uniformly mixed for 1: 6 with the ratio of the volume (L) of activating solution
Afterwards, place 10 minutes in the vacuum tank that vacuum is -0.1MPa, subsequently mixture is transferred in high pressure resistant reactor, in
150 DEG C of 120 min of insulation；Most at last activation products are filtered, and filter cake is dried 2h at 100 DEG C.
As shown in figure 1, being the scanning electron microscope of modified activated carbon (b) prepared by activated carbon raw material (a) and the embodiment of the present invention 3
Contrast photo.
Embodiment 4
The ratio of configuration quality is 1（25% ammonia）∶0.05（Activator promotor ammonium sulfate）Activating solution, stirring, treat that solid is completely dissolved
；By commercially available activated carbon raw material, by quality（kg）After being uniformly mixed for 1: 8 with the ratio of the volume (L) of activating solution, in
Vacuum be -0.1MPa vacuum tank in place 20 minutes, subsequently mixture is transferred in high pressure resistant reactor, in 150 DEG C
It is incubated 240 min；Most at last activation products are filtered, and filter cake is dried 2h at 100 DEG C.
In the present invention, activator promotor is not limited solely to ammonium sulfate, violent chemical reaction does not occur with activated carbon and can provide
The ammonium salt of nitrogen-atoms all can be used.
Application examples 1
Activated carbon prepared by above-mentioned example 3 is in active substance: acetylene black: PVDF=85: 10: 5 ratio is mixed, and prepares
Into electrode slice, with 6M KOH solution as electrolyte, knob is assembled into using the barrier film used in known double layer capacitor jointly
Button ultracapacitor.Tested under different scanning rates using cyclic voltammetry, as a result as shown in Fig. 3.The graphite
The cyclic voltammetry curve for changing activated carbon electrodes is maintained to preferable rectangle in the case where the height of 50 mV/s sweeps speed, illustrates its tool
There is very high high rate performance.
Application examples 2
Activated carbon prepared by above-mentioned example 4 is in active substance: acetylene black: PVDF=85: 10: 5 ratio is mixed, and prepares
Into electrode slice, with 6M KOH solution as electrolyte, knob is assembled into using the barrier film used in known double layer capacitor jointly
Button ultracapacitor.The test of AC impedance is carried out under room temperature in CHI660D electrochemical workstations, its test result is shown in figure
4.Through the activated carbon for preparing of the invention compared with non-modified raw material, its resistance value is substantially reduced.
Above example explanation, adopts the present invention to prepare with excellent electrochemical by raw material of commercially available activated carbon
The modified active Carbon Materials of energy.
Claims (2)
1. a kind of modifying method of activated carbon for electrochemical energy storing device, comprises the following steps：
（1）Prepare nitrogenous activating solution：Inorganic ammonium salt is added to filling in the container that mass percent concentration is 15～25% ammonia simultaneously
Stirring, treats that solid is completely dissolved；Wherein ammonia and the mass ratio of ammonium salt are 1:（0.05～0.2）；
（2）By activated carbon raw material powder and step（1）The volume of nitrogenous activating solution is by 1 kg:（3～8）The ratio mix homogeneously of L,
Subsequently mixture is placed in 10～20 minutes in the vacuum tank that vacuum is -0.1MPa；
（3）By step（2）Activated carbon mixed liquor be transferred in pressure reactor, in 80～150oActivated under C, during insulation
Between 2～4 hours, be subsequently cooled to room temperature；
（4）By step（3）Gained mixed liquor after filtering, is dried to filter cake, obtains final product the work for electrochemical energy storing device
Property charcoal.
2. a kind of modifying method of activated carbon for electrochemical energy storing device according to claim 1, it is characterised in that：Institute
It is ammonium sulfate or ammonium chloride to state inorganic ammonium salt.
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| CN201611133261.6A CN106587059B (en) | 2016-12-10 | 2016-12-10 | A kind of modifying method of activated carbon for electrochemical energy storing device |
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| CN201611133261.6A CN106587059B (en) | 2016-12-10 | 2016-12-10 | A kind of modifying method of activated carbon for electrochemical energy storing device |
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| CN106587059A true CN106587059A (en) | 2017-04-26 |
| CN106587059B CN106587059B (en) | 2018-12-25 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011176043A (en) * | 2010-02-23 | 2011-09-08 | Calgon Carbon Japan Kk | Activated carbon for electric double layer capacitor |
| CN103785353A (en) * | 2014-01-18 | 2014-05-14 | 山西潞安矿业(集团)有限责任公司 | Method for preparing composite activated carbon-zeolite material from coal gangue |
| CN105126597A (en) * | 2015-07-30 | 2015-12-09 | 沈阳三聚凯特催化剂有限公司 | Refinery waste gas desulfurizer, preparation method and applications thereof |
| CN105692611A (en) * | 2016-03-21 | 2016-06-22 | 中国科学院理化技术研究所 | Preparation method of biomass activated carbon rich in nitrogen and oxygen |
| CN105869925A (en) * | 2016-05-10 | 2016-08-17 | 扬州大学 | Preparation method of nitrogen-doped CA/PAN-based carbon microsphere electrode material |
| WO2016163899A1 (en) * | 2015-04-09 | 2016-10-13 | Nicolaus Copernicus University In Torun | Activated carbons with a high nitrogen content and a high electric conduction and the method of manufacturing activated carbons, in particular the method of manufacturing electrodes |
-
2016
- 2016-12-10 CN CN201611133261.6A patent/CN106587059B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011176043A (en) * | 2010-02-23 | 2011-09-08 | Calgon Carbon Japan Kk | Activated carbon for electric double layer capacitor |
| CN103785353A (en) * | 2014-01-18 | 2014-05-14 | 山西潞安矿业(集团)有限责任公司 | Method for preparing composite activated carbon-zeolite material from coal gangue |
| WO2016163899A1 (en) * | 2015-04-09 | 2016-10-13 | Nicolaus Copernicus University In Torun | Activated carbons with a high nitrogen content and a high electric conduction and the method of manufacturing activated carbons, in particular the method of manufacturing electrodes |
| CN105126597A (en) * | 2015-07-30 | 2015-12-09 | 沈阳三聚凯特催化剂有限公司 | Refinery waste gas desulfurizer, preparation method and applications thereof |
| CN105692611A (en) * | 2016-03-21 | 2016-06-22 | 中国科学院理化技术研究所 | Preparation method of biomass activated carbon rich in nitrogen and oxygen |
| CN105869925A (en) * | 2016-05-10 | 2016-08-17 | 扬州大学 | Preparation method of nitrogen-doped CA/PAN-based carbon microsphere electrode material |
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