CN108584944A - A kind of preparation method of the ultracapacitor rich nitrogen grading porous carbon electrode material of high-specific surface area - Google Patents
A kind of preparation method of the ultracapacitor rich nitrogen grading porous carbon electrode material of high-specific surface area Download PDFInfo
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- CN108584944A CN108584944A CN201810665361.6A CN201810665361A CN108584944A CN 108584944 A CN108584944 A CN 108584944A CN 201810665361 A CN201810665361 A CN 201810665361A CN 108584944 A CN108584944 A CN 108584944A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
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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
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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 discloses a kind of ultracapacitor preparation methods of the rich nitrogen grading porous carbon electrode material of high-specific surface area.Using ethylenediamine tetraacetic acid disodium zinc salt salt as carbon source, it is carbonized under inert gas protection in 700 1000 °C of constant temperature, is prepared using pickling, washing.The rich nitrogen grading porous carbon electrode material of prepared high-specific surface area has high-ratio surface concurrently（1500‑2800 m2g‑1）, flourishing graded porous structure（Hole holds 1.2~3.6 cm3g‑1）, be rich in nitrogen（Nitrogen content 1.8~12.6%）, there is excellent capacitive property and high rate performance for electrode material for super capacitor.The method method is simple, and environmental-friendly, cost is relatively low.
Description
Technical field
The present invention relates to electrode material for super capacitor technical fields, more particularly to a kind of ultracapacitor Gao Bibiao
The preparation method of the rich nitrogen grading porous carbon electrode material of area.
Background technology
Ultracapacitor is also known as electrochemical capacitor, is that a kind of performance is new between physical capacitor and secondary cell
Type energy-storage travelling wave tube.Ultracapacitor has higher energy density relative to physical capacitor, has work(relative to secondary cell
The advantages that rate density is high, have extended cycle life, charge/discharge rates are fast, and safety and environmental protection is pollution-free, sends out in electric vehicle, renewable resource
The fields such as electricity, mobile device power supply and new and high technology weapon have a wide range of applications.
Absorbent charcoal material has higher specific surface, high electric conductivity, preferable chemical stability and resourceful, valence
The features such as lattice are cheap becomes the widest electrode material of current supercapacitor applications.Rich nitrogen Carbon Materials are due in porous charcoal
A certain amount of nitrogen-atoms is doped in structure, the electrode material for ultracapacitor can not only improve electrode and electrolyte
Wellability, can also generate pseudo-capacitance makes the specific capacitance of porous charcoal greatly improve.Pore-size distribution is to influence Carbon Materials capacitive property
Key factor, Microporous Carbon（Aperture<2nm）High specific surface is conducive to obtain big specific capacitance, mesoporous carbon（2 ~ 50nm of aperture）Hair
The meso-hole structure reached is conducive to obtain excellent high rate performance, and high ratio can then be taken into account by having micropore and mesoporous grading-hole Carbon Materials concurrently
The high rate performance of capacitance and friendship is the developing direction of carbon electrode of super capacitor material.
Grading-hole charcoal preparation method mainly has double-template method, template-activation method, biological material carbonization-activation method at present
Deng.Wherein template-activation method obtains the extensive concern of people, and Xiaojun He et al. are using pitch as carbon precursor, three oxidations two
Iron is hard template, and KOH is that activator is prepared for surface area 761-1330 m2g-1Grading-hole Carbon Materials（J. Mater. Chem.
A, 2013, 1, 9440-9448）.For Bin Xu et al. using sucrose as carbon source, nano-calcium carbonate is hard template, and NaOH is activation
Agent is prepared for 2032 m of specific surface area2g-1Carbon Materials, in 6 mol L-1Specific capacitance is 245 F g in KOH electrolyte-1（New
J. Chem. 2014, 38, 5509-5514）.Although these methods can get grading-hole Carbon Materials, preparation section is complicated,
Cost is higher.
There are mainly two types of the preparation methods of rich nitrogen porous charcoal.One is high temperature ammoniated treatment is carried out to porous charcoal, in its table
Face introduces nitrogen-atoms.Another kind is to make porous charcoal that can retain raw material in preparation process using nitrogen containing polymer polymer as raw material
Part nitrogen-atoms in structure.102757034 A's of Patent No. CN《A kind of preparation method of richness nitrogen porous carbon material》It is open
By edetate（Tetrasodium salt, disodium salt, sodium magnesium salts, molysite, calcium salt or manganese salt）High temperature pyrolysis, washing prepare rich nitrogen
The method of porous charcoal can prepare nitrogen content 1.6~15.5%, specific surface area 600-2000m2/ g, hole hold 0.3~1.8cm3/g
Rich nitrogen porous carbon material, but the aperture of the Carbon Materials prepared using these edetates as carbon source is mainly 2 nm or less
Micropore be unfavorable for improving high rate performance of the Carbon Materials under high current.For example, being cracked by carbon source of tetrasodium ethylenediamine tetraacetate
1171 m of Carbon Materials specific surface area highest of preparation2g-1, 0.05 A g of current density-1When specific capacitance 245 F g-1, current density
Increase to 20 A g-1When, specific capacitance is 188 F g-1（Electrochimica Acta. 2013, 98, 176-182）.
The present invention proposes that, using ethylenediamine tetraacetic acid disodium zinc salt salt as raw material, prepared by direct step Pintsch process have micropore-
The new method of the rich nitrogen Carbon Materials of mesoporous graded porous structure.It is different as presoma from using other edetates, second two
The nano zine oxide that amine tetraacethyl disodium zinc generates during Pintsch process act not only as hard template formed it is mesoporous, and
A part of charcoal can be etched away with charcoal reaction selectivity in 700 °C or more nano zine oxides to form abundant micropore, because
And the porous charcoal prepared has micropore and mesoporous, specific surface concurrently and hole holds up to 1500-2800 m respectively2g-1With 1.2~3.6
cm3g-1, all greatly improved compared with preceding method for its specific capacity of electrode material for super capacitor and high-rate performance.With second two
Amine tetraacethyl disodium zinc directly prepares the rich nitrogen grading porous carbon electrode material of high-specific surface area for carbon source high temperature pyrolysis and has no domestic
There are document and patent report outside.
Invention content
The purpose of the present invention is to provide a kind of simplicity to prepare the rich nitrogen grading porous charcoal of ultracapacitor high-specific surface area
The method of electrode material.Preparation method is as follows：
Using ethylenediamine tetraacetic acid disodium zinc salt salt as raw material, under inert gas protection by it in 700-1000 °C of constant temperature carbonization 1-
10 h obtain nitrogen content 1.8~12.6%, specific surface area 1500-2800 m using pickling, washing2g-1, hole hold 1.2~3.6
cm3g-1 , micropore and the mesoporous all flourishing nitrogen grading porous Carbon Materials of richness.
Wherein, inert gas used is the gaseous mixture of nitrogen, argon gas or both.
Wherein, acid pickling aqueous solution is the mixture of one or both of hydrochloric acid, sulfuric acid, nitric acid acid, acid
A concentration of 0.5-5 mol/L of aqueous solution.
The principle of the present invention is：Ethylenediamine tetraacetic acid disodium zinc salt salt carries out Pintsch process process under inert atmosphere protection
In, zinc oxide occupy-place pore-creating in carbon network structure as hard template of generation forms meso-hole structure, while at 700 °C or more
At a high temperature of zinc oxide can be with charcoal reaction selectivity etch away sections charcoal atom, to generate a large amount of micropores, washing removes ZnO
Porous charcoal will be obtained after (or Zn).Due to containing nitrogen in the ethylenediamine tetraacetic acid disodium zinc salt as carbon source, in high temperature
Also part nitrogen has been remained in the network structure of pyrolysis product charcoal.Therefore, use ethylenediamine tetraacetic acid disodium zinc salt can for carbon source
Prepare the rich nitrogen grading porous carbon electrode material of high-specific surface area.Due to having high-specific surface area and flourishing classifying porous knot concurrently
Structure is applied to electrode material for super capacitor, has high specific capacitance and excellent high rate performance concurrently.
Advantages of the present invention includes：
（1）Prepared Carbon Materials have high-ratio surface concurrently（1500-2800 m2g-1）, flourishing graded porous structure（Hole holds 1.2
~3.6 cm3g-1）, be rich in nitrogen（Nitrogen content 1.8~12.6%）, there is excellent electricity for electrode material for super capacitor
Capacitive energy and high rate performance.
（2）Preparation method according to the present invention have it is simple for process, only need a step charing can prepare high-ratio surface
The rich nitrogen grading porous carbon electrode material of product, and with the features such as environmental-friendly, energy expenditure is low.
Description of the drawings
Fig. 1 is the pore size distribution curve of Carbon Materials prepared by the embodiment of the present invention 1.
Fig. 2 is the transmission electron microscope photo of Carbon Materials prepared by the embodiment of the present invention 1.
Fig. 3 is the XPS spectrum of Carbon Materials prepared by the embodiment of the present invention 1.
Specific implementation mode
Following example will be further described the present invention, but not thereby limiting the invention.
Embodiment 1
Take 25g ethylenediamine tetraacetic acid disodium zinc salts salt 700 °C of 10 h of charing in a nitrogen atmosphere.Carbonizing production is successively with 0.5
Mol/L hydrochloric acid and water washing, you can porous charcoal charcoal is made.The test of nitrogen adsorption desorption shows that the absorbent charcoal material specific surface area is
1530m2g-1, hole holds 1.23 cm3g-1, mesoporous rate is 50.5%.Pore size distribution curve is as shown in Figure 1, illustrate the Carbon Materials prepared
Aperture include 1-2nm micropore and 10-30nm it is mesoporous.Transmission electron microscope is as shown in Fig. 2, can be observed abundant mesoporous and micro-
Hole.XPS tests nitrogen distribution as shown in figure 3, the nitrogen content of the material is 7.46%.Above-mentioned material is pressed into active material：Acetylene
It is black：PTFE=85:10:5 ratio carries out being prepared by mixing into electrode slice, in 6 mol L-1KOH electrolyte in carry out two electrodes perseverance
Flow charge and discharge and cyclic voltammetry, when 0.1 A/g of current density calculates specific capacitance by discharge curve and is up to 280 F g-1, electricity
Current density increases to 50 A g-1When, specific capacitance still keeps 230 F g-1, show that it has height ratio capacity and excellent forthright again concurrently
Energy.
Embodiment 2
Take 30g ethylenediamine tetraacetic acid disodium zinc salts salt in argon gas and nitrogen mixed gas volume ratio（1:1）The lower 850 °C of constant temperature of atmosphere
Carbonize 2h.Carbonizing production is successively with 3 mol/L nitric acid and water washing, you can porous charcoal charcoal is made.The absorbent charcoal material specific surface
Product is 2268m2g-1, hole holds 2.6 cm3g-1, mesoporous rate 53.4%, nitrogen content 6.71%.It is measured according to the test method of embodiment 1
Specific capacitance is calculated by discharge curve when 0.1 A/g of its current density and is up to 330F g-1, current density increases to 50 A g-1When,
Specific capacitance still keeps 270 F g-1, show that it has height ratio capacity and excellent high rate performance concurrently.
Embodiment 3
Take 40g ethylenediamine tetraacetic acid disodium zinc salts salt 1000 °C of charing 1h under an argon atmosphere.Carbonizing production passes through 2mol/L salt
The mixing acid elution of acid and 1mol/L sulfuric acid, water washing can be prepared by porous charcoal.The porous carbon material specific surface area is 2680
m2g-1, hole holds 3.0 cm3g-1, mesoporous rate 59.4%.2.23 % of nitrogen content.It is close that its electric current is measured according to the test method of embodiment 1
Specific capacitance is calculated by discharge curve when spending 0.1 A/g and is up to 326F g-1, current density increases to 50 A g-1When, specific capacitance is still
Keep 289 F g-1, specific capacity and high rate performance protrude.
Embodiment 4
Take 23g ethylenediamine tetraacetic acid disodium zinc salts salt 900 °C of charing 5h in a nitrogen atmosphere.Carbonizing production passes through 3 mol/L sulfuric acid
Washing, water washing can be prepared by porous charcoal.The porous carbon material specific surface area is 2390 m2g-1, hole holds 2.38 cm3g-1, it is situated between
Porosity 62.1%, 3.12 % of nitrogen content.
Claims (3)
1. a kind of ultracapacitor preparation method of the rich nitrogen grading porous carbon electrode material of high-specific surface area, it is characterised in that：
Using ethylenediamine tetraacetic acid disodium zinc salt salt as raw material, it is carbonized 1-10 h in 700-1000 °C of constant temperature under inert gas protection,
Nitrogen content 1.8~12.6%, specific surface area 1500-2800 m are obtained using pickling, washing2g-1, hole hold 1.2~3.6 cm3g-1 , micropore and the mesoporous all flourishing nitrogen grading porous Carbon Materials of richness.
2. according to a kind of preparation of the rich nitrogen grading porous carbon electrode material of high-specific surface area of ultracapacitor described in claim 1
Method, it is characterised in that：Inert gas used is the gaseous mixture of nitrogen, argon gas or both.
3. according to a kind of preparation of the rich nitrogen grading porous carbon electrode material of high-specific surface area of ultracapacitor described in claim 1
Method, it is characterised in that：Acid pickling aqueous solution is the mixture of one or both of hydrochloric acid, sulfuric acid, nitric acid acid, acid
A concentration of 0.5-5 mol/L of property aqueous solution.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109761216A (en) * | 2019-03-22 | 2019-05-17 | 大连理工大学 | A kind of general, method that porous carbon materials are prepared based on organic zinc salt |
| CN110028069A (en) * | 2019-04-18 | 2019-07-19 | 河南师范大学 | A kind of preparation method of the advanced carbon electrode material of multi-stage porous for supercapacitor |
| CN110182800A (en) * | 2019-07-15 | 2019-08-30 | 天津工业大学 | A kind of method for preparation of active carbon based on ethylene diamine tetraacetic acid sylvite |
| CN110280293A (en) * | 2019-07-15 | 2019-09-27 | 天津工业大学 | A kind of preparation method of water process advanced oxidation composite catalyst |
| CN114023573A (en) * | 2021-11-02 | 2022-02-08 | 南京信息工程大学 | Preparation method of triazinyl aza two-dimensional electrode material |
| CN117247011A (en) * | 2023-11-16 | 2023-12-19 | 成都达奇科技股份有限公司 | Preparation method of active carbon with high benzene series adsorption rate and active carbon |
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| CN102757034A (en) * | 2012-08-07 | 2012-10-31 | 中国人民解放军63971部队 | Method for preparing nitrogen-rich porous carbon material |
| CN103272559A (en) * | 2013-05-21 | 2013-09-04 | 北京化工大学 | Application of porous carbon electrode material in electrosorb technology |
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Patent Citations (2)
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| CN102757034A (en) * | 2012-08-07 | 2012-10-31 | 中国人民解放军63971部队 | Method for preparing nitrogen-rich porous carbon material |
| CN103272559A (en) * | 2013-05-21 | 2013-09-04 | 北京化工大学 | Application of porous carbon electrode material in electrosorb technology |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109761216A (en) * | 2019-03-22 | 2019-05-17 | 大连理工大学 | A kind of general, method that porous carbon materials are prepared based on organic zinc salt |
| CN110028069A (en) * | 2019-04-18 | 2019-07-19 | 河南师范大学 | A kind of preparation method of the advanced carbon electrode material of multi-stage porous for supercapacitor |
| CN110182800A (en) * | 2019-07-15 | 2019-08-30 | 天津工业大学 | A kind of method for preparation of active carbon based on ethylene diamine tetraacetic acid sylvite |
| CN110280293A (en) * | 2019-07-15 | 2019-09-27 | 天津工业大学 | A kind of preparation method of water process advanced oxidation composite catalyst |
| CN114023573A (en) * | 2021-11-02 | 2022-02-08 | 南京信息工程大学 | Preparation method of triazinyl aza two-dimensional electrode material |
| CN114023573B (en) * | 2021-11-02 | 2023-11-10 | 南京信息工程大学 | Preparation method of triazinyl aza two-dimensional electrode material |
| CN117247011A (en) * | 2023-11-16 | 2023-12-19 | 成都达奇科技股份有限公司 | Preparation method of active carbon with high benzene series adsorption rate and active carbon |
| CN117247011B (en) * | 2023-11-16 | 2024-04-09 | 成都达奇科技股份有限公司 | Preparation method of active carbon with high benzene series adsorption rate and active carbon |
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