CN106587059B - A kind of modifying method of activated carbon for electrochemical energy storing device - Google Patents
A kind of modifying method of activated carbon for electrochemical energy storing device Download PDFInfo
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- CN106587059B CN106587059B CN201611133261.6A CN201611133261A CN106587059B CN 106587059 B CN106587059 B CN 106587059B CN 201611133261 A CN201611133261 A CN 201611133261A CN 106587059 B CN106587059 B CN 106587059B
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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
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- 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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Abstract
The invention proposes a kind of modifying method of activated carbon for electrochemical energy storing device, comprising the following steps: after mixing active carbon powder with nitrogenous activating solution, is placed in pressure-resistant reaction kettle, in 80~150oC is activated, and is filtered, is dried, and high-performance electric chemistry energy storage device modified active Carbon Materials are obtained.Present invention process is easy, pollution-free, and the product prepared has big specific surface area and excellent chemical property.
Description
Technical field
The present invention relates to a kind of modifying method of activated carbon for electrochemical energy storing device, belong in electrochemical energy storing device
Electrode material field.
Technical background
Electrochemical energy storing device has the characteristics that the service life is long, power is big, environmentally protective and easy to carry, as electronic equipment
It is with a wide range of applications with the power supply of automobile.Battery and supercapacitor as important electrochemical energy storing device mainly by
Electrode, electrolyte, diaphragm, end plate, lead and encapsulation form, and chemical property is mainly determined by the performance of electrode material,
Middle active carbon material is one of most common negative electrode material.
The hydrophobic macromolecules that active carbon material is made of numerous not localization carbon atoms, are unfavorable for dispersing in a solvent,
Which limits the good characteristics for being used as electrode material possessed by the material itself.In addition, not because of raw material and preparation process
Together, cause commercial active carbon material spread in performance uneven.Therefore, activated carbon is modified, i.e., is introduced in activated carbon surface new
Hydrophilic nitrogenous, oxygen functional group, the wellability that can not only improve carbon can also impart to its additional physical chemistry function,
Improve their practical application performances.
The method for being currently modified processing to activated carbon mainly has (1) heating, the Cryogenic air in 300~350 DEG C
In carry out aoxidize or disposed in 800~1000 DEG C of high temperature inert atmosphere；(2) plasma processing method；(3) microwave method；(4) add
Add activator, activator mainly has concentrated nitric acid, concentrated ammonia liquor, urea, melamine etc..There are equipment valuableness, energy consumption for above method
Height has the various problems such as certain environment pollutes or performance raising is unobvious, limits its application industrially.Therefore, overcome existing
There is the deficiency of technology, the method for modifying for developing a kind of active carbon for electrochemical energy storing device plays an important role.
Summary of the invention
The present invention provides a kind of modifying method of activated carbon for electrochemical energy storing device, is raw material warp 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 for electrochemistry and stores up
The electrode material of energy device uses.
The technical solution adopted by the present invention are as follows: a kind of method of modifying of the active carbon for electrochemical energy storing device, including
Following steps:
(1) it prepares nitrogenous activating solution: Inorganic Ammonium is added to filling in the container that mass percent concentration is 15~25% ammonium hydroxide
Salt simultaneously stirs, and is completely dissolved to solid；Wherein the mass ratio of ammonium hydroxide and ammonium salt is 1: (0.05~0.2)；Pay attention to ammonium salt
Additional amount cannot be greater than its solubility when configuring temperature；
(2) by the volume of activated carbon raw material powder and step (1) nitrogenous activating solution in 1 kg: the ratio mixing of (3~8) L
Uniformly, then mixture is placed in the vacuum tank that vacuum degree is -0.1MPa 10~20 minutes；
(3) the active carbon mixed liquor of step (2) is transferred in pressure-resistant reaction kettle, is activated at 80~150 DEG C, protected
It 2~4 hours warm time, then cools to room temperature；
(4) after filtering by mixed liquor obtained by step (3), filter cake is dried to get for electrochemical energy storing device
Active carbon.
In above-mentioned technical proposal, the filtrate that step (4) obtains, can Reusability after concentration is deployed.
In above-mentioned technical proposal, the inorganic ammonium salt is activator promotor, preferential ammonium sulfate or ammonium chloride.
The utility model has the advantages that compared with the prior art, the advantages of the present invention are as follows:
(1) present invention can be greatly reduced the dosage of ammonium hydroxide as activator promotor and be improved the nitrogen in solution using inorganic ammonium salt
Content, and then mitigate corrosion and problem of environmental pollution of the alkali to equipment in subsequent activation process；Using vacuum impregnation containing nitrogen solution
Active carbon improves the uniformity of activating solution and active particle exposure level and distribution, accelerates diffusion of the solution in active carbon
Adsorption process；Third, impregnate active carbon mixed solution be separated by filtration after, filtrate can multiple Reusability；
(2) present invention strengthens activation modification process using nitrogenous activating solution-hydro-thermal combination method, improves production technology, section
About energy consumption reduces pollution, and the active carbon material pore structure development that high specific area is made is more mature, is used for electrochemical energy accumulator
Chemical property is good when the electrode material of part.
In conclusion the present invention is using active carbon as raw material, it is living 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
Learning energy storage device field has wide application prospect.
Detailed description of the invention
The scanning electron microscope of modified activated carbon (b) prepared by Fig. 1 activated carbon raw material (a) and the embodiment of the present invention 3 is to contrasting
Piece；
Fig. 2 activated carbon raw material (a), active carbon are prepared through ammonium hydroxide activation modification (b) and the embodiment of the present invention 3 at room temperature
Modified activated carbon (c) infrared spectrum comparison diagram；
Fig. 3 is the cyclic voltammetry curve of activated carbon electrodes prepared by the embodiment of the present invention 1；
Fig. 4 is the electrochemical AC impedance pair of active carbon (b) prepared by the embodiment of the present invention 2 and activated carbon raw material (a)
Than figure.
Specific embodiment
The following examples will be further described the present invention, but not thereby limiting the invention.
In following embodiment, the ammonia concn being related to refers to mass percent concentration.
Embodiment 1
The ratio between configuration quality be 1(15% ammonium hydroxide): 0.2(activator promotor ammonium sulfate) activating solution, stirring, it is complete to solid
Dissolution；Using commercially available active carbon as raw material, it is uniformly mixed by the ratio between volume (L) of quality (kg) and activating solution for 1: 4
Afterwards, it is placed in the vacuum tank that vacuum degree is -0.1MPa 10 minutes, then mixture is transferred in high pressure resistant reaction kettle, in 100
DEG C heat preservation 120 min；Finally activation products are filtered, filter cake is in 100 DEG C of dry 2h.
Embodiment 2
The ratio between the amount for configuring substance is 1(20% ammonium hydroxide): 0.15(activator promotor ammonium sulfate) activating solution, stirring, to solid
It is completely dissolved；By commercially available activated carbon raw material, it is stirred by the ratio between volume (L) of quality (kg) and activating solution for 1: 4
After even, it is placed in the vacuum tank that vacuum degree is -0.1MPa 15 minutes, then mixture is transferred in high pressure resistant reaction kettle, in
80 DEG C of 180 min of heat preservation；Finally activation products are filtered, filter cake is in 100 DEG C of dry 2h.
Embodiment 3
The ratio between the amount for configuring substance is 1(25% ammonium hydroxide): 0.1(activator promotor ammonium sulfate) activating solution, stirring, to solid
It is completely dissolved；By commercially available activated carbon raw material, it is stirred by the ratio between volume (L) of quality (kg) and activating solution for 1: 6
After even, place 10 minutes in the vacuum tank that vacuum degree is -0.1MPa, then mixture is transferred in high pressure resistant reaction kettle,
In 150 DEG C of 120 min of heat preservation；Finally activation products are filtered, filter cake is in 100 DEG C of dry 2h.
As shown in Figure 1, being the scanning electron microscope of the modified activated carbon (b) of activated carbon raw material (a) and the preparation of the embodiment of the present invention 3
Compare photo.
Embodiment 4
The ratio between configuration quality be 1(25% ammonium hydroxide): 0.05(activator promotor ammonium sulfate) activating solution, stirring, it is complete to solid
Dissolution；By commercially available activated carbon raw material, it is uniformly mixed by the ratio between volume (L) of quality (kg) and activating solution for 1: 8
Afterwards, it places 20 minutes in the vacuum tank that vacuum degree is -0.1MPa, then mixture is transferred in high pressure resistant reaction kettle, in
150 DEG C of 240 min of heat preservation；Finally activation products are filtered, filter cake is in 100 DEG C of dry 2h.
In the present invention, activator promotor is not limited solely to ammonium sulfate, does not occur acutely to chemically react and can provide with active carbon
The ammonium salt of nitrogen-atoms all can be used.
Application examples 1
Active carbon prepared by above-mentioned example 3 is in active material: acetylene black: PVDF=85: 10: 5 ratio mixes,
It is prepared into electrode slice, using 6M KOH solution as electrolyte, is assembled jointly using the diaphragm used in known double layer capacitor
At button-shaped supercapacitor.It is tested under different scanning rates using cyclic voltammetry, as a result as shown in Fig. 3.It should
Preferable rectangle, explanation can still be maintained in the case where the height of 50 mV/s sweeps speed in the cyclic voltammetry curve of graphitization activated carbon electrodes
It is with very high high rate performance.
Application examples 2
Active carbon prepared by above-mentioned example 4 is in active material: acetylene black: PVDF=85: 10: 5 ratio mixes,
It is prepared into electrode slice, using 6M KOH solution as electrolyte, is assembled jointly using the diaphragm used in known double layer capacitor
At button-shaped supercapacitor.The test of AC impedance is carried out under room temperature in CHI660D electrochemical workstation, test result is shown in
Fig. 4.By active carbon prepared by the present invention compared with non-modified raw material, impedance value is substantially reduced.
Above embodiments explanation, uses the present invention that can prepare by raw material of commercially available active carbon with excellent electrochemical
The modified active Carbon Materials of energy.
Claims (2)
1. a kind of modifying method of activated carbon for electrochemical energy storing device, comprising the following steps:
(1) it prepares nitrogenous activating solution: inorganic ammonium salt is added simultaneously to filling in the container that mass percent concentration is 15~25% ammonium hydroxide
Stirring, is completely dissolved to solid；Wherein the mass ratio of ammonium hydroxide and ammonium salt is 1: (0.05~0.2)；
(2) by the volume of activated carbon raw material powder and step (1) nitrogenous activating solution in 1 kg: the ratio of (3~8) L is uniformly mixed,
Then mixture is placed in the vacuum tank that vacuum degree is -0.1MPa 10~20 minutes；
(3) the active carbon mixed liquor of step (2) is transferred in pressure-resistant reaction kettle, in 80~150oIt is activated under C, when heat preservation
Between 2~4 hours, then cool to room temperature；
(4) after filtering by mixed liquor obtained by step (3), filter cake is dried to get 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
Stating inorganic ammonium salt is ammonium sulfate or ammonium chloride.
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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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