CN108529591B - A kind of porous carbon nanosheet and its preparation method and application of B, N codope - Google Patents
A kind of porous carbon nanosheet and its preparation method and application of B, N codope Download PDFInfo
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- CN108529591B CN108529591B CN201810459486.3A CN201810459486A CN108529591B CN 108529591 B CN108529591 B CN 108529591B CN 201810459486 A CN201810459486 A CN 201810459486A CN 108529591 B CN108529591 B CN 108529591B
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- chloroethyl
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- amine
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 90
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000002135 nanosheet Substances 0.000 title claims abstract description 75
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- VKPPFDPXZWFDFA-UHFFFAOYSA-N 2-chloroethanamine Chemical compound NCCCl VKPPFDPXZWFDFA-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 19
- CXEAPDZVXCSARE-UHFFFAOYSA-N (2-chloroethylamino)boronic acid Chemical compound B(NCCCl)(O)O CXEAPDZVXCSARE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007772 electrode material Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000003990 capacitor Substances 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000004327 boric acid Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 15
- 238000004090 dissolution Methods 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000005255 carburizing Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract 1
- 239000003575 carbonaceous material Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 230000004913 activation Effects 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- -1 amido boric acid Chemical compound 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- C01B32/15—Nano-sized carbon materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The present invention discloses a kind of B, the porous carbon nanosheet of N codope and preparation method thereof, using two (2- chloroethyl) amine hydrochlorates as raw material, by being mixed with two (2- chloroethyl) amine with lye.Then, two (2- chloroethyl) amido boric acid are obtained in two (2- chloroethyl) amine and acid reaction.Then, (2- chloroethyl) amido boric acid is pyrolyzed under nitrogen protection, successfully prepares B, the porous carbon nanometer sheet material of N codope.Porous carbon nanosheet B prepared by the present invention, N content is high, large specific surface area；When the electrode material for super capacitor being used as, capacitive property is high, and good rate capability has extended cycle life.This method is easy to operate, economical and efficient, it can be achieved that the porous carbon nanosheet of B, N codope industrialized production.
Description
Technical field
The present invention designs a kind of carbon material and preparation method thereof, in particular to a kind of B for ultracapacitor electrode material,
Porous carbon nanosheet of N codope and preparation method thereof belongs to carbon material technical field.
Background technique
Porous carbon nanosheet (CNS) material refers to using carbon as basic framework, with the novel of porous super-thin sheet-shaped structure
Two-dimensional material.This kind of material usually has flourishing hole, high specific surface area, ultra-thin two-dimensional sheet structure, good leads
Electrically, excellent physics and the advantages that chemical stability, make its heterogeneous catalysis, bio-sensing, gas absorption with separate and
Many fields such as energy storage have stronger application potential.
The type and quantity of pure CNS surface functional group are all less, and the high-specific surface area of porous carbon materials is not in the application
It can be fully used.B/N atom and carbon atom are very close in structure, can be by controlling preparation process, with B/N atom
Replace carbon atom, B/N atom is introduced in porous carbon materials, the pore structure of adjustable porous carbon materials changes material
Surface composition, the electric conductivity for improving the hydrophily of material, reinforcing material, greatly expand porous carbon materials applies model
It encloses.On the other hand, compared with traditional blocky porous carbon materials, two-dimentional carbon nanosheet is due to its unique two-dimensional structure and exposure
Active site on surface causes it to have short ion transmission path and very high electron mobility, to be allowed in super capacitor
Outstanding chemical property is shown in the application of device and Anode of lithium cell.Therefore, in order to meet needs, ultra-thin two-dimensional sheet
The atom doped construction and B/N of structure is a kind of method for simply and effectively changing carbon material chemical property.
Currently, the preparation method of doping porous carbon nanometer sheet material mainly has direct activation method and template method.Activation method is
At high temperature pyrolysis have layer structure and heteroatomic presoma, then be carbonized after presoma and chemical activating agent (such as
KOH, H3PO4, ZnCl2) mixing after high-temperature activation.It is cumbersome using this method preparation process, need the activation using strong corrosive
Agent leads to increased costs, is unfavorable for industrialized production.Template method is using template (such as SiO2, FeCl3, montmorillonite (MT)
Deng) it is used as template or reactor, and high temperature pyrolysis is carried out after being sufficiently mixed containing heteroatomic presoma.By template to carbon nanometer
The structure snd size of piece carry out control accurate.But the template preparation process of some special constructions is complicated, is unfavorable for carbon nanosheet
Low cost production.
Summary of the invention
The purpose of the present invention is to provide a kind of B, porous carbon nanosheet of N codope and preparation method thereof.This method is
Based on liquid reactive self-assembly method.Compared with currently used activation method and template, this method has easy to operate, environment
The friendly, remarkable advantages such as low energy consumption, since this method avoid the corrosivity of complicated equipment and chemical activation, so having can
Scalability and sustainability.The porous carbon nanometer sheet material of prepared B, N codope has great in supercapacitor
Application value.
The first embodiment provided according to the present invention provides a kind of B, the porous carbon nanosheet of N codope.
The porous carbon nanosheet of a kind of B, N codope, it is by including prepared by following preparation method: first by two
(2- chloroethyl) amine hydrochlorate and alkali reaction obtain two (2- chloroethyl) amine, then that two (2- chloroethyl) amine and boric acid are anti-
Two (2- chloroethyl) amido boric acid should be obtained, then two (2- chloroethyl) amido boric acid are carbonized, obtain B, N codope
Porous carbon nanosheet.
Preferably, the porous carbon nanosheet of the B, N codope has 1000m2g-1To 2500m2g-1, preferably
1200m2g-1To 2300m2g-1, more preferable 1500m2g-1To 2000m2g-1BET specific surface area.
Preferably, the porous carbon nanosheet of the B, N codope have 20-100nm, preferably 25-80nm, more preferably
The average thickness of 30-60nm.
Preferably, the porous carbon nanosheet of the B, N codope has 2.0% to 6.0% B content (at%), it is excellent
Select 3.0% to 5.5% B content (at%), more preferable 3.6% to 5.0% B content (at%).
Preferably, the porous carbon nanosheet of the B, N codope has 2.0% to 4.0% N content (at%), it is excellent
Select 2.5% to 3.5% N content (at%), more preferable 2.6% to 3.0% N content (at%).
In the present invention, as the B, when the porous carbon nanosheet of N codope is used as the electrode material of capacitor, in 0.5A
g-1Current density under, specific capacitance be greater than 260F g-1, preferably specific capacitance is greater than 280F g-1, more preferable specific capacitance is greater than 320F
g-1。
Second of the embodiment provided according to the present invention, provide it is a kind of prepare B, the porous carbon nanosheet of N codope
Method.
It is a kind of to prepare B, the method for the porous carbon nanosheet of N codope or prepare B described in the first embodiment, N
The method of the porous carbon nanosheet of codope, method includes the following steps:
(1) two (2- chloroethyl) amine are prepared: two (2- chloroethyl) amine hydrochlorates and alkali being mixed, is dissolved in water, stirs
It mixes, stratification, will be washed after the faint yellow sticky liquid separation of lower layer, it is dry to obtain two (2- chloroethyl) amine；
(2) prepare two (2- chloroethyl) amido boric acid: two (2- chloroethyl) amine and boric acid that step (1) is obtained are mixed
It closes, in a solvent, ethyl alcohol is added after completion of the reaction in oil bath heating for dissolution, and it is cooling after dissolution, crystallization is precipitated, obtains two (2-
Chloroethyl) amido boric acid；
(3) be carbonized: two (2- chloroethyl) amido boric acid that step (2) is obtained are placed in carbide furnace, are carbonized；It will
Material washing after carbonization, it is finally that product is dry to constant weight, obtain B, the porous carbon nanosheet of N codope.
In the present invention, step (1) specifically: in water by two (2- chloroethyl) amine hydrochlorates and alkali mixed dissolution, In
1-5h (preferably 2-4h) is stirred at room temperature, 0.2-6h (preferably 0.5-4h) is stood and is layered afterwards, lower layer is faint yellow sticky
Neutrality is washed with distilled water to after liquid separation, vacuum drying obtains two (2- chloroethyl) amine.
In the present invention, step (2) specifically: two (2- chloroethyl) amine and boric acid mixed dissolution for obtaining step (1)
In organic solvent, body is added after completion of the reaction in the oil bath 1-5h (preferably 2-3h) under 50-90 DEG C (preferably 60-80 DEG C)
Fraction is greater than 90% ethyl alcohol (preferably volume fraction is greater than 95% ethyl alcohol), pours out, natural cooling while hot, crystallization is precipitated, obtains
To two (2- chloroethyl) amido boric acid.
In the present invention, step (3) specifically: two (2- chloroethyl) the amido boric acid for obtaining step (2) are placed in carbonization
In furnace, be warming up under the protection of inert gas carburizing temperature (such as 600-100 DEG C, preferably 650-950 DEG C, more preferable 700-
900 DEG C) be carbonized (such as 1-5h, preferably 1.5-3h)；Material after carbonization is washed with distilled water to neutrality, finally by product
Drying obtains B, the porous carbon nanosheet of N codope to constant weight.
Preferably, (2- chloroethyl) amine hydrochlorate and alkali mass ratio are 1:1-6, preferably 1:2-5 two in step (1), more
It is preferred that 1:2.5-4.
Preferably, the alkali is NaOH or KOH, preferably KOH.
Preferably, (2- chloroethyl) amine and boric acid mass ratio are 1:1-8, preferably 1:2-6 two in step (2), more preferably
1:3-5。
Preferably, the organic solvent is DMF or DMSO.
Preferably, the rate to heat up in step (3) is 1~10 DEG C of min-1, preferably 2~8 DEG C of min-1, more excellent
It is selected as 3~6 DEG C of min-1。
Preferably, the retort is high temperature process furnances, the inert gas is argon gas or nitrogen.
The third embodiment provided according to the present invention provides a kind of B, the purposes of the porous carbon nanosheet of N codope.
The porous carbon nanosheet of B described in the first embodiment, N codope or as described in second of embodiment
The purposes of the porous carbon nanosheet of B prepared by method, N codope, B, the porous carbon nanosheet of N codope be used as capacitor or
The electrode material of supercapacitor.
In the present invention, B is prepared, the method for the porous carbon nanosheet of N codope is based on liquid reactive self-assembly method.
Compared with currently used activation method and template, this method has the remarkable advantages such as be simple to operate and friendly to environment, low energy consumption,
Since this method avoid the corrosivity of complicated equipment and chemical activation, so having scalability and sustainability.It is made
The porous carbon nanometer sheet material of standby B, N codope has great application value in supercapacitor.
In the present invention, the average thickness refers to is measured using scanning electron microscope (SEM) and Atomic Mechanics microscope (AFM)
Lamellar spacing average value.
In the present invention, two (2- chloroethyl) amine hydrochlorates in the step of preparation method (1) and alkali mixed dissolution are in water
In, there is no limit for two concentration of (2- chloroethyl) amine hydrochlorate and alkali in water.In general, two (2- chloroethyl) amine hydrochlorates
Mass concentration in water is 1-20%, preferably 2-10%.The mass concentration of alkali in water is 5-30%, preferably 6-
20%.
In the present invention, the separation in the step of preparation method (1) can first use separate modes all in the prior art,
Such as liquid separation separation, extraction and separation, filters pressing or suction filtration separation etc..
In the present invention, two (2- chloroethyl) amine in the step of preparation method (2) and boric acid mixed dissolution are in solvent
In, there is no limit for two (2- chloroethyl) amine and the concentration of boric acid in a solvent.In general, amine is in a solvent for two (2- chloroethyls)
Mass concentration is 1-15%, preferably 2-10%.Mass concentration is 5-40%, preferably 10-30% to boric acid in a solvent.
In the present invention, ethyl alcohol is added in the step of preparation method (2): using excessive ethanol washing, it is therefore an objective to wash away
Unreacted raw material and impurity.
In the present invention, reaction principle and flow chart are as shown in Figure 7.
Compared with prior art, technical solution of the present invention has following advantageous effects:
1, the method for the present invention simple process, preparation process, can be real without using certain moduli plate and corrosive activator
The existing large-scale preparation of low cost.
2, the method for the present invention can be matched by feed change, preparation condition realizes content of heteroatoms to carbon nanosheet, piece
The regulation of thickness degree and aperture structure.
3, obtained the more hole carbon nanosheet large specific surface area, even aperture distribution, B, N content is high, as super electricity
When the electrode material of container, there is excellent chemical property.
Detailed description of the invention
Fig. 1 is B prepared by example 1, the scanning electron microscope (SEM) photograph of the porous carbon nanosheet of N codope；
Fig. 2 is B prepared by example 1, the N2 adsorption/desorption curve of the porous carbon nanosheet of N codope；
Fig. 3 is B prepared by example 1, the porous carbon nanosheet pore size distribution curve of N codope；
Fig. 4 is B prepared by example 1, the XPS map of the porous carbon nanosheet of N codope；
Fig. 5 is B prepared by example 1, the porous carbon nanosheet of N codope, cyclic voltammetric when applied to supercapacitor
Test chart；
Fig. 6 is B prepared by example 1, the porous carbon nanosheet of N codope, constant current charge and discharge when applied to supercapacitor
Electrical measurement attempts；
Fig. 7 is present invention preparation B, the reaction principle and flow chart of the porous carbon nanosheet of N codope.
Specific embodiment
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that following instance is served only for
The present invention is further described, should not be understood as limiting the scope of the invention, and person skilled in art can basis
Foregoing invention content makes some nonessential modifications and adaptations to the present invention.
The structural characterization of biological carbon passes through N in following instance2(Micromeritics TriStar II 3020) is adsorbed to survey
Examination.Specific surface area uses adsorption isotherm according to Brunauer-Emmett-Teller (BET) theoretical calculation, pore-size distribution (PSD)
The absorption of line props up and Barrett-Joyner-Halenda (BJH) model is used to calculate.
Raw material, reagent and the instrument used in embodiment:
Two (2- chloroethyl) amine hydrochlorates: Aladdin chemical reagents corporation, AR.
Sodium hydroxide: Aladdin chemical reagents corporation, AR
Isopropanol: Aladdin chemical reagents corporation, AR
Boric acid: Aladdin chemical reagents corporation, AR.
HCl: Tianjin Fu Yu Fine Chemical Co., Ltd, AR.
Polytetrafluoroethylene (PTFE): Aladdin chemical reagents corporation, 60wt%.
N2: the Hongyuan Zhong Tai, Hunan gas Co., Ltd.
Nickel foam: Changsha Liyuan New Material Co., Ltd..
Scanning electron microscope (SEM): Japanese JEOL company, S-4800
X-ray photoelectron spectroscopy (XPS): Thermo Fischer Scient Inc., Britain, K-Alpha 1063.
Specific surface area and Porosimetry: Micromeritics company, the U.S., Tristar II 3020.
Electrochemical workstation: Shanghai Chen Hua Instrument Ltd., CHI760D.
When porous carbon nanosheet is as electrode material for super capacitor in following instance electrode the production method is as follows:
Use above-mentioned made porous carbon nanosheet for active material, conductive carbon black is conductive agent, ptfe emulsion
(PTFE, 60wt%) is binder, and using nickel foam as collector.These three substances are scattered in ethyl alcohol in the ratio of 80:10:10
In, ultrasound is stirred so that being uniformly mixed, and is transferred to mortar grinder, is evaporated into muddy to ethyl alcohol, it is uniformly applied to foam nickel sheet.
Thus 5min compacting is kept with 10MPa pressure after made electrode is slightly dried, it is spare to place into dry 12h in 120 DEG C of baking ovens.Carbon
The load capacity of material activity substance is respectively in 4mg cm-2Left and right.
Biological carbon is as follows as the electrode material progress electrochemical test method of supercapacitor in following instance:
The capacitive property of single electrode is tested using CHI760D electrochemical workstation three-electrode system, wherein to electrode
For platinum electrode, Hg/HgO is reference electrode, and 6M KOH solution is electrolyte.This example mainly use cyclic voltammetry (CV),
The methods of constant current charge-discharge (GC) and electrochemical impedance spectroscopy (EIS) carry out electrochemical property test.The circulation of single electrode
Volt-ampere test voltage range is set as -1~0V.The current density of charge-discharge test is arranged in 0.5~20A g-1, and voltage range
For -1~0V.Cyclic charging and discharging test is carried out by two electrode systems, and current density is set as 1A g-1, wherein to electrode and ginseng
It is same electrode than electrode, operating voltage range is set as 0~1V.
The specific capacitance of carbon material passes through the electric discharge branch of constant current charge-discharge, and calculates according to the following formula:
Cg=I/ (mdV/dt)
Wherein I is constant current, and m is the quality of active material, and dV/dt is according to the discharge curve for removing voltage drop part
Calculate resulting slope.
Example 1
By (2- chloroethyl) amine hydrochlorate of 5g bis- and 15g NaOH mixed dissolution in 100mL water, it is stirred at room temperature
2.5h is layered after standing 1h, will be washed with distilled water to neutrality after the faint yellow sticky liquid liquid separation of lower layer, vacuum drying obtains
Two (2- chloroethyl) amine.
Then, by (2- chloroethyl) amine of 2g bis- and 8g boric acid mixed dissolution in 50mL DMF, the oil bath at 70 DEG C
2.5h is added 95% ethyl alcohol, pours out while hot, natural cooling after completion of the reaction, and crystallization is precipitated, obtains two (2- chloroethyl) amidos
Boric acid.
Then, 1g bis- (2- chloroethyl) amido boric acid is placed in high temperature process furnances, in N2Protection under with 4 DEG C/min
Rate be warming up to 800 DEG C, be carbonized 2h.Material after carbonization is washed with distilled water to neutrality, finally dries product to constant weight,
Obtain the B of 0.28g, the porous carbon nanosheet of N codope.
Prepared porous carbon nanosheet has the porous nano chip architecture of class graphene, nanometer obtained as shown in Figure 1
The thickness overwhelming majority of piece all concentrates in the range of 20-50nm；Such as two BET specific surface area of figure is up to 1732m2g-1, total hole body
Product is 1.12cm3g-1；As shown in figure 3, the aperture of material is largely micropore, a part be it is mesoporous, small part is macropore, is had
Ideal pore-size distribution；As shown in figure 4, B content is 3.2at%, N content 2.8at%.Electrode material as supercapacitor
When material, as shown in figure 4, the doping of N atom, material has apparent fake capacitance, as shown in figure 5, in 0.5Ag due to B-1Electricity
Under current density, the specific capacitance for adulterating carbon nanosheet is 321F g-1。
Example 2
By (2- chloroethyl) amine hydrochlorate of 5g bis- and 20g KOH mixed dissolution in 100mL water, 4h is stirred at room temperature,
It is layered after standing 2h, neutrality will be washed with distilled water to after the faint yellow sticky liquid liquid separation of lower layer, vacuum drying obtains two
(2- chloroethyl) amine.
Then, by (2- chloroethyl) amine of 2g bis- and 6g boric acid mixed dissolution in 50mL DMF, the oil bath 3h at 80 DEG C,
After completion of the reaction, 90% ethyl alcohol is added, pours out while hot, natural cooling, crystallization is precipitated, obtains two (2- chloroethyl) amido boric acid
With extraction and rotary evaporation obtains two (2- chloroethyl) amido boric acid.
Then, 1g bis- (2- chloroethyl) amido boric acid is placed in high temperature process furnances, in N2Protection under with 3 DEG C/min
Rate be warming up to 700 DEG C, be carbonized 3h.Material after carbonization is washed with distilled water to neutrality, finally dries product to constant weight,
Obtain the B of 0.31g, the porous carbon nanosheet of N codope.
Porous carbon nanosheet BET specific surface area prepared by example 2 is 1412m2g-1, total pore volume 0.83cm3g-1, B
Content is 3.8at%, N content 2.9at%.When adulterating the electrode material as supercapacitor of carbon nanosheet, In
0.5Ag-1Current density under, specific capacitance be 299F g-1。
Example 3
By (2- chloroethyl) amine hydrochlorate of 5g bis- and 10g NaOH mixed dissolution in 100mL water, it is stirred at room temperature
2h is layered after standing 0.8h, will be washed with distilled water to neutrality after the faint yellow sticky liquid liquid separation of lower layer, vacuum drying obtains
Two (2- chloroethyl) amine.
Then, by (2- chloroethyl) amine of 2g bis- and 10g boric acid mixed dissolution in 50mL DMF, the oil bath at 60 DEG C
2.5h is added 90% ethyl alcohol, pours out while hot, natural cooling after completion of the reaction, and crystallization is precipitated, obtains two (2- chloroethyl) amidos
Boric acid.
Then, 1g bis- (2- chloroethyl) amido boric acid is placed in high temperature process furnances, in N2Protection under with 6 DEG C/min
Rate be warming up to 900 DEG C, be carbonized 2h.Material after carbonization is washed with distilled water to neutrality, finally dries product to constant weight,
Obtain the B of 0.19g, the porous carbon nanosheet of N codope.
Porous carbon nanosheet BET specific surface area prepared by example 3 is 1532m2g-1, total pore volume 0.94cm3g-1, B
Content is 3.0at%, N content 2.4at%.When electrode material as supercapacitor, in 0.5Ag-1Current density under,
The specific capacitance for adulterating carbon nanosheet is 286F g-1。
Claims (12)
1. the porous carbon nanosheet of a kind of B, N codope, it is by including prepared by following preparation method: first by two
(2- chloroethyl) amine hydrochlorate and alkali reaction obtain two (2- chloroethyl) amine, then that two (2- chloroethyl) amine and boric acid are anti-
Two (2- chloroethyl) amido boric acid should be obtained, then two (2- chloroethyl) amido boric acid are carbonized, obtain B, N codope
Porous carbon nanosheet；
Wherein: the porous carbon nanosheet of the B, N codope has 1000m2g-1To 2500m2g-1BET specific surface area；It is described
The porous carbon nanosheet of B, N codope has the average thickness of 20-100nm；The porous carbon nanosheet of the B, N codope has
2.0% to 6.0% B content；The porous carbon nanosheet of the B, N codope has 2.0% to 4.0% N content.
2. the porous carbon nanosheet of B according to claim 1, N codope, it is characterised in that: the B, N codope it is more
Hole carbon nanosheet has 1200m2g-1To 2300m2g-1BET specific surface area；The porous carbon nanosheet of the B, N codope has
The average thickness of 25-80nm；The porous carbon nanosheet of the B, N codope has 3.0% to 5.5% B content；The B, N
The porous carbon nanosheet of codope has 2.5% to 3.5% N content.
3. the porous carbon nanosheet of B according to claim 1, N codope, it is characterised in that: the B, N codope it is more
Hole carbon nanosheet has 1500m2g-1To 2000m2g-1BET specific surface area；The porous carbon nanosheet of the B, N codope has
The average thickness of 30-60nm；The porous carbon nanosheet of the B, N codope has 3.6% to 5.0% B content；The B, N
The porous carbon nanosheet of codope has 2.6% to 3.0% N content.
4. the porous carbon nanosheet of B according to any one of claim 1-3, N codope, it is characterised in that: when described
When the porous carbon nanosheet of B, N codope is used as the electrode material of capacitor, in 0.5A g-1Current density under, specific capacitance is big
In 260F g-1。
5. the porous carbon nanosheet of B according to claim 4, N codope, it is characterised in that: as the B, N codope
When porous carbon nanosheet is used as the electrode material of capacitor, in 0.5A g-1Current density under, specific capacitance be greater than 280F g-1。
6. the porous carbon nanosheet of B according to claim 4, N codope, it is characterised in that: as the B, N codope
When porous carbon nanosheet is used as the electrode material of capacitor, in 0.5A g-1Current density under, specific capacitance be greater than 320F g-1。
7. a kind of prepare B of any of claims 1-6, the method for the porous carbon nanosheet of N codope, this method packet
Include following steps:
(1) two (2- chloroethyl) amine are prepared: in water by two (2- chloroethyl) amine hydrochlorates and alkali mixed dissolution, at room temperature
1-5h is stirred, is layered after standing 0.2-6h, neutrality, vacuum will be washed with distilled water to after the faint yellow sticky liquid separation of lower layer
It is dried to obtain two (2- chloroethyl) amine；
(2) two (2- chloroethyl) amido boric acid are prepared: two (2- chloroethyl) amine and boric acid mixed dissolution that step (1) is obtained
In organic solvent, the oil bath 1-5h at 50-90 DEG C is added volume fraction and is greater than 90% ethyl alcohol, fall while hot after completion of the reaction
Out, natural cooling is precipitated crystallization, obtains two (2- chloroethyl) amido boric acid；
(3) be carbonized: two (2- chloroethyl) amido boric acid that step (2) is obtained are placed in carbide furnace, in the protection of inert gas
Under be warming up to carburizing temperature and be carbonized；Material after carbonization is washed with distilled water to neutrality, finally dries product to constant weight,
Obtain B, the porous carbon nanosheet of N codope；
Wherein: (2- chloroethyl) amine hydrochlorate and alkali mass ratio are 1:1-6 two in step (1)；The alkali is NaOH or KOH；Step
Suddenly (2- chloroethyl) amine and boric acid mass ratio are 1:1-8 two in (2)；The organic solvent is DMF or DMSO；It is risen in step (3)
The rate of temperature is 1~10 DEG C of min-1；The carbide furnace is high temperature process furnances, and the inert gas is argon gas or nitrogen.
8. according to the method described in claim 7, time of repose is it is characterized by: mixing time is 2-4h in step (1)
0.5-4h；In step (2), in organic solvent with boric acid mixed dissolution by two (2- chloroethyl) amine of step (1) acquisition, In
Oil bath 2-3h at 60-80 DEG C is added volume fraction and is greater than 95% ethyl alcohol after completion of the reaction；Carburizing temperature is 600- in step (3)
100 DEG C, the time being carbonized is 1-5h.
9. according to the method described in claim 8, it is characterized by: in step (3) carburizing temperature be 650-950 DEG C, carry out carbon
The time of change is 1.5-3h.
10. the method according to any one of claim 7-9, it is characterised in that: (2- chloroethyl) amine two in step (1)
Hydrochloride and alkali mass ratio are 1:2-5；The alkali is KOH；And/or
(2- chloroethyl) amine and boric acid mass ratio are 1:2-6 two in step (2)；And/or
The rate to heat up in step (3) is 2~8 DEG C of min-1。
11. according to the method described in claim 10, it is characterized by: (2- chloroethyl) amine hydrochlorate and alkali two in step (1)
Mass ratio is 1:2.5-4；And/or
(2- chloroethyl) amine and boric acid mass ratio are 1:3-5 two in step (2)；And/or
The rate to heat up in step (3) is 3~6 DEG C of min-1。
12. B described in any one of claim 1-6, the porous carbon nanosheet of N codope or by appointing in claim 7-11
B prepared by what one method, the purposes of the porous carbon nanosheet of N codope, it is characterised in that: B, N codope it is porous
Carbon nanosheet is used as the electrode material of capacitor or supercapacitor.
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