CN108529591A - 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
- Publication number
- CN108529591A CN108529591A CN201810459486.3A CN201810459486A CN108529591A CN 108529591 A CN108529591 A CN 108529591A CN 201810459486 A CN201810459486 A CN 201810459486A CN 108529591 A CN108529591 A CN 108529591A
- Authority
- CN
- China
- Prior art keywords
- chloroethyls
- porous carbon
- carbon nanosheet
- amine
- codope
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 78
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000002135 nanosheet Substances 0.000 title claims abstract description 64
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 34
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 claims abstract description 59
- 150000001412 amines Chemical class 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000004327 boric acid Substances 0.000 claims abstract description 34
- -1 amido boric acid Chemical compound 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000007772 electrode material Substances 0.000 claims abstract description 12
- 239000003990 capacitor Substances 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 13
- 235000019441 ethanol Nutrition 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 238000004090 dissolution Methods 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 9
- 238000003763 carbonization Methods 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000013459 approach Methods 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000005255 carburizing Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 claims 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical class ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000003575 carbonaceous material Substances 0.000 description 10
- 230000004913 activation Effects 0.000 description 8
- 239000000126 substance Substances 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
- 238000012360 testing method Methods 0.000 description 5
- 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
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 239000011149 active material Substances 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
- CXEAPDZVXCSARE-UHFFFAOYSA-N (2-chloroethylamino)boronic acid Chemical compound B(NCCCl)(O)O CXEAPDZVXCSARE-UHFFFAOYSA-N 0.000 description 2
- VKPPFDPXZWFDFA-UHFFFAOYSA-N 2-chloroethanamine Chemical compound NCCCl VKPPFDPXZWFDFA-UHFFFAOYSA-N 0.000 description 2
- 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
- 150000001721 carbon Chemical group 0.000 description 2
- 230000008859 change Effects 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
- 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
- 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
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 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
- 125000004429 atom Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 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
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 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
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration 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
- 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
- 238000002156 mixing Methods 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
- 239000012779 reinforcing material Substances 0.000 description 1
- 235000009566 rice Nutrition 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)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (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 codopes and preparation method thereof, using two (2- chloroethyls) amine hydrochlorates as raw material, by being mixed with two (2- chloroethyls) amine with lye.Then, two (2- chloroethyls) amido boric acid are obtained in two (2- chloroethyls) amine and acid reaction.Then, (2- chloroethyls) amido boric acid is pyrolyzed under nitrogen protection, successfully prepares B, the porous carbon nanometer sheet material of N codopes.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
A kind of carbon material of present invention design and preparation method thereof, more particularly to a kind of B for ultracapacitor electrode material,
Porous carbon nanosheet of N codopes and preparation method thereof belongs to carbon material technical field.
Background technology
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 detach and
Many fields such as energy storage have stronger application potential.
The type and quantity of pure CNS surface functional groups 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 atoms are very close in structure with carbon atom, can be by controlling preparation process, with B/N atoms
Replace carbon atom, B/N atoms are introduced in porous carbon materials, the pore structure of porous carbon materials can be adjusted, change material
The electric conductivity of surface composition, the hydrophily for improving 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 are a kind of simple and effective methods for changing carbon material chemical property.
Currently, the preparation method of doping porous carbon nanometer sheet material mainly has direct activation method and masterplate method.Activation method is
Pyrolysis has layer structure and heteroatomic presoma at high temperature, presoma and chemical activating agent after being then carbonized (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 causes cost to increase, and is unfavorable for industrialized production.Masterplate method is using template (such as SiO2, FeCl3, montmorillonite (MT)
Deng) it is used as template or reactor, and carry out high temperature pyrolysis after being sufficiently mixed containing heteroatomic presoma.Carbon is received by template
The structure snd size of rice piece carry out control accurate.But the masterplate preparation process of some special constructions is complicated, is unfavorable for carbon nanometer
The low cost production of piece.
Invention content
The purpose of the present invention is to provide a kind of B, porous carbon nanosheet of N codopes 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 with can
Autgmentability and sustainability.The porous carbon nanometer sheet material of prepared B, N codope has great on ultracapacitor
Application value.
According to the first embodiment provided by the invention, a kind of B, the porous carbon nanosheet of N codopes are provided.
The porous carbon nanosheet of a kind of B, N codope, it is by including prepared by following preparation method：First by two
(2- chloroethyls) amine hydrochlorate and alkali reaction obtain two (2- chloroethyls) amine, then that two (2- chloroethyls) amine and boric acid are anti-
Two (2-chloroethyl) amido boric acid should be obtained, then two (2- chloroethyls) amido boric acid are carbonized, obtain B, N codopes
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 30-60 nm.
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 codopes is used as the electrode material of capacitor, in 0.5A
g-1Current density under, specific capacitance be more than 260F g-1, preferably specific capacitance is more than 280F g-1, more preferable specific capacitance is more than 320F
g-1。
According to second of embodiment provided by the invention, provide it is a kind of preparing B, the porous carbon nanosheet of N codopes
Method.
It is a kind of to prepare B, the method for the porous carbon nanosheet of N codopes or prepare B, N described in the first embodiment
The method of the porous carbon nanosheet of codope, this approach includes the following steps：
(1) two (2- chloroethyls) amine are prepared：Two (2- chloroethyls) amine hydrochlorates and alkali are 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- chloroethyls) amine；
(2) two (2- chloroethyls) amido boric acid are prepared：Two (2- chloroethyls) amine that step (1) is obtained are mixed with boric acid
It closes, in a solvent, ethyl alcohol is added after completion of the reaction in oil bath heating for dissolving, cooling after dissolving, and crystallization is precipitated, obtains two (2-
Chloroethyl) amido boric acid；
(3) it is carbonized：Two (2- chloroethyls) amido boric acid that step (2) obtains are placed in carbide furnace, are carbonized；It will
Material washing after carbonization, product is finally dried to constant weight, obtain B, the porous carbon nanosheet of N codopes.
In the present invention, step (1) is specially：In water by two (2- chloroethyls) amine hydrochlorates and alkali mixed dissolution, exist
1-5h (preferably 2-4h) is stirred at room temperature, is stood 0.2-6h (preferably 0.5-4h) 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- chloroethyls) amine.
In the present invention, step (2) is specially：Two (2- chloroethyls) amine that step (1) is obtained and boric acid mixed dissolution
In organic solvent, body is added after completion of the reaction in oil bath 1-5h (preferably 2-3h) under 50-90 DEG C (preferably 60-80 DEG C)
Fraction is more than 90% ethyl alcohol (preferably volume fraction is more than 95% ethyl alcohol), pours out while hot, natural cooling, crystallization is precipitated, obtains
To two (2- chloroethyls) amido boric acid.
In the present invention, step (3) is specially：Two (2- chloroethyls) amido boric acid that step (2) obtains are placed in carbonization
In stove, 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) it is carbonized (such as 1-5h, preferably 1.5-3h)；Material after carbonization is washed with distilled water to neutrality, finally will production
Object is dried to constant weight, and B, the porous carbon nanosheet of N codopes are obtained.
Preferably, (2- chloroethyls) amine hydrochlorate and alkali mass ratio are 1 two in step (1):1-6, preferably 1:2-5, more
It is preferred that 1:2.5-4.
Preferably, the alkali is NaOH or KOH, preferably KOH.
Preferably, (2- chloroethyls) amine and boric acid mass ratio are 1 two in step (2):1-8, preferably 1:2-6, 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.
According to the third embodiment provided by the invention, a kind of B, the purposes of the porous carbon nanosheet of N codopes are provided.
The porous carbon nanosheet of B described in the first embodiment, N codope or described in second of embodiment
The purposes of the porous carbon nanosheet of B prepared by method, N codope, B, the porous carbon nanosheets of N codopes be used as capacitor or
The electrode material of ultracapacitor.
In the present invention, B is prepared, the method for the porous carbon nanosheet of N codopes is to be 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 on ultracapacitor.
In the present invention, the average thickness refers to being measured using scanning electron microscope (SEM) and Atomic Mechanics microscope (AFM)
Lamellar spacing average value.
In the present invention, two (2- chloroethyls) 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- chloroethyls) amine hydrochlorate and alkali in water.In general, two (2- chloroethyls) 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, press filtration or suction filtration separation etc..
In the present invention, two (2- chloroethyls) amine in the step of preparation method (2) and boric acid mixed dissolution are in solvent
In, there is no limit with the concentration of boric acid in a solvent for two (2-chloroethyl) amine.In general, two (2- chloroethyls) amine are in solvent
Middle 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)：It is washed using excessive ethyl alcohol, 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 scheme of the present invention has following advantageous effects：
1, the method for the present invention is simple for process, and preparation process, can be real without using certain moduli plate and corrosive activator
Existing low cost is large-scale to be prepared.
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 and control of layer thickness 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.
Description of the drawings
Fig. 1 is B prepared by example 1, the scanning electron microscope (SEM) photograph of the porous carbon nanosheet of N codopes；
Fig. 2 is B prepared by example 1, the N2 adsorption/desorption curves of the porous carbon nanosheet of N codopes；
Fig. 3 is B prepared by example 1, the porous carbon nanosheet pore size distribution curve of N codopes；
Fig. 4 is B prepared by example 1, the XPS collection of illustrative plates of the porous carbon nanosheet of N codopes；
Fig. 5 is B prepared by example 1, and the porous carbon nanosheet of N codopes is applied to cyclic voltammetric when ultracapacitor
Test chart；
Fig. 6 is B prepared by example 1, and the porous carbon nanosheet of N codopes is applied to constant current charge and discharge when ultracapacitor
Electrical measurement attempts；
Fig. 7 is that the present invention prepares B, the reaction principle and flow chart of the porous carbon nanosheet of N codopes.
Specific implementation mode
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- chloroethyls) 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 Hongyuans Zhong Tai, Hunan gas Co., Ltd.
Nickel foam：Changsha Liyuan New Material Co., Ltd..
Scanning electron microscope (SEM)：Japanese JEOL companies, S-4800
X-ray photoelectron spectroscopy (XPS)：Thermo Fischer Scient Inc. of Britain, K-Alpha 1063.
Specific surface area and Porosimetry：Micromeritics companies of the U.S., Tristar II 3020.
Electrochemical workstation：Shanghai Chen Hua Instrument Ltd., CHI760D.
The production method of electrode is as follows when porous carbon nanosheet is as electrode material for super capacitor in following instance：
Use above-mentioned made porous carbon nanosheet for active material, conductive carbon black is conductive agent, ptfe emulsion
(PTFE, 60 wt%) are binder, and using nickel foam as collector.These three substances press 80:10:10 ratio is scattered in second
In alcohol, ultrasound is stirred so that being uniformly mixed, mortar grinder is transferred to, waits for that ethyl alcohol evaporates into muddy, it is uniformly applied to nickel foam
Piece.Thus 5min compactings are kept with 10MPa pressure after made electrode is slightly dried, it is standby to place into dry 12h in 120 DEG C of baking ovens
With.The load capacity of carbon material active material is respectively in 4mg cm-2Left and right.
Biological carbon is as follows as the electrode material progress electrochemical test method of ultracapacitor in following instance：
The capacitive property of single electrode is tested using CHI760D electrochemical workstation three-electrode systems, wherein to electrode
For platinum electrode, Hg/HgO is reference electrode, and 6M KOH solutions are 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 cycle 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 is calculated by the electric discharge branch of constant current charge-discharge according to 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 the slope of gained.
Example 1
By (2- chloroethyls) amine hydrochlorates of 5g bis- and 15g NaOH mixed dissolutions in 100mL water, it is stirred at room temperature
2.5 h are layered after standing 1h, will be washed with distilled water to neutrality after the faint yellow sticky liquid liquid separation of lower layer, be dried in vacuo
To two (2- chloroethyls) amine.
Then, by (2- chloroethyls) amine of 2g bis- and 8g boric acid mixed dissolution in 50mL DMF, the oil bath 2.5 at 70 DEG C
H is added 95% ethyl alcohol, pours out while hot, natural cooling after completion of the reaction, and crystallization is precipitated, obtains two (2- chloroethyls) amido boron
Acid.
Then, 1g bis- (2- chloroethyls) 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 codopes.
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 is mesoporous, and 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 ultracapacitor
When material, as shown in figure 4, due to B, the doping of N atoms, material has apparent fake capacitance, as shown in figure 5, in 0.5 Ag-1Electricity
Under current density, the specific capacitance for adulterating carbon nanosheet is 321F g-1。
Example 2
By (2- chloroethyls) amine hydrochlorates of 5g bis- and 20g KOH mixed dissolutions 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- chloroethyls) amine.
Then, by (2- chloroethyls) 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- chloroethyls) amido boric acid
Two (2- chloroethyls) amido boric acid are obtained with extraction and rotary evaporation.
Then, 1g bis- (2- chloroethyls) 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 codopes.
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 ultracapacitor of carbon nanosheet,
0.5Ag-1Current density under, specific capacitance be 299F g-1。
Example 3
By (2- chloroethyls) amine hydrochlorates of 5g bis- and 10g NaOH mixed dissolutions 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- chloroethyls) 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- chloroethyls) amine
Ylboronic acid.
Then, 1g bis- (2- chloroethyls) 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 codopes.
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 ultracapacitor, in 0.5Ag-1Current density under,
The specific capacitance for adulterating carbon nanosheet is 286F g-1。
Claims (10)
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- chloroethyls) amine hydrochlorate and alkali reaction obtain two (2- chloroethyls) amine, then that two (2- chloroethyls) amine and boric acid are anti-
Two (2- chloroethyls) amido boric acid should be obtained, then two (2- chloroethyls) amido boric acid are carbonized, obtain B, N codopes
Porous carbon nanosheet.
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 1000m2g-1To 2500m2g-1, preferably 1200m2g-1To 2300m2g-1, more preferable 1500m2g-1Extremely
2000m2g-1BET specific surface area；And/or
The porous carbon nanosheet of the B, N codope has the average thickness of 20-100nm, preferably 25-80nm, more preferable 30-60nm
Degree.
3. the porous carbon nanosheet of B according to claim 1 or 2, N codope, it is characterised in that：The B, N codope
Porous carbon nanosheet have 2.0% to 6.0% B content (at%), preferably 3.0% to 5.5% B content (at%), more
It is preferred that 3.6% to 5.0% B content (at%)；With
The porous carbon nanosheet of the B, N codope have 2.0% to 4.0% N content (at%), preferably 2.5% to 3.5%
N content (at%), more preferable 2.6% to 3.0% N content (at%).
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, preferably specific capacitance is more than 280F g-1, more preferable specific capacitance is more than 320F g-1。
5. a kind of preparing B, B, N described in any one of the method for the porous carbon nanosheet of N codopes or preparation claim 1-4
The method of the porous carbon nanosheet of codope, this approach includes the following steps：
(1) two (2- chloroethyls) amine are prepared：Two (2- chloroethyls) amine hydrochlorates and alkali are mixed, are dissolved in water, are stirred, it is quiet
Layering is set, will be washed after the faint yellow sticky liquid separation of lower layer, it is dry to obtain two (2- chloroethyls) amine；
(2) two (2- chloroethyls) amido boric acid are prepared：Two (2- chloroethyls) amine that step (1) obtains are mixed with boric acid, it is molten
In a solvent, ethyl alcohol is added after completion of the reaction in oil bath heating to solution, cooling after dissolving, and crystallization is precipitated, obtains two (2- chloroethenes
Base) amido boric acid；
(3) it is carbonized：Two (2- chloroethyls) amido boric acid that step (2) obtains are placed in carbide furnace, are carbonized；It will carbonization
Material washing afterwards, product is finally dried to constant weight, obtain B, the porous carbon nanosheet of N codopes.
6. according to the method described in claim 5, it is characterized in that：Step (1) is specially：By two (2- chloroethyls) amine salt acid
In water, 1-5h (preferably 2-4h) is stirred at room temperature in salt and alkali mixed dissolution, after standing 0.2-6h (preferably 0.5-4h)
Layering will be washed with distilled water to neutrality after the faint yellow sticky liquid separation of lower layer, and vacuum drying obtains two (2- chloroethyls)
Amine.
7. according to the method described in claim 5, it is characterized in that：Step (2) is specially：Two (the 2- that step (1) is obtained
Chloroethyl) amine and boric acid mixed dissolution in organic solvent, oil bath 1-5h is (preferably under 50-90 DEG C (preferably 60-80 DEG C)
2-3h), after completion of the reaction, volume fraction is added and is more than 90% ethyl alcohol (preferably volume fraction is more than 95% ethyl alcohol), falls while hot
Go out, natural cooling, crystallization is precipitated, obtains two (2- chloroethyls) amido boric acid.
8. according to the method described in claim 5, it is characterized in that：Step (3) is specially：Two (the 2- that step (2) is obtained
Chloroethyl) amido boric acid is placed in carbide furnace, be warming up under the protection of inert gas carburizing temperature (such as 600-100 DEG C, it is excellent
Select 650-950 DEG C, more preferable 700-900 DEG C) it is carbonized (such as 1-5h, preferably 1.5-3h)；Material distillation after carbonization
Product is finally dried to constant weight to neutrality, obtains B, the porous carbon nanosheet of N codopes by water washing.
9. according to the method described in any one of claim 5-8, it is characterised in that：(2- chloroethyls) amine salt two in step (1)
Hydrochlorate and alkali mass ratio are 1:1-6, preferably 1:2-5, more preferable 1:2.5-4；The alkali is NaOH or KOH, preferably KOH；And/or
(2- chloroethyls) amine and boric acid mass ratio are 1 two in step (2):1-8, preferably 1:2-6, more preferable 1:3-5；It is described to have
Solvent is DMF or DMSO；And/or
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 preferably 3~6Cmin-1；Institute
It is high temperature process furnances to state retort, and the inert gas is argon gas or nitrogen.
10. the porous carbon nanosheet of the B described in any one of claim 1-4, N codope or by claim 5-9 appoint
B prepared by what one method, the purposes of the porous carbon nanosheet of N codopes, it is characterised in that：B, N codope it is porous
Carbon nanosheet is used as the electrode material of capacitor or ultracapacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810459486.3A CN108529591B (en) | 2018-05-15 | 2018-05-15 | A kind of porous carbon nanosheet and its preparation method and application of B, N codope |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810459486.3A CN108529591B (en) | 2018-05-15 | 2018-05-15 | A kind of porous carbon nanosheet and its preparation method and application of B, N codope |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108529591A true CN108529591A (en) | 2018-09-14 |
| CN108529591B CN108529591B (en) | 2019-11-22 |
Family
ID=63477133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810459486.3A Expired - Fee Related CN108529591B (en) | 2018-05-15 | 2018-05-15 | A kind of porous carbon nanosheet and its preparation method and application of B, N codope |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108529591B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109592665A (en) * | 2019-01-21 | 2019-04-09 | 兖矿集团有限公司 | A kind of preparation method of nanoporous carbon materials |
| CN110902678A (en) * | 2019-11-01 | 2020-03-24 | 宁夏大学 | Method for preparing sulfur-oxygen co-doped porous carbon based on paper |
| CN111410186A (en) * | 2020-03-16 | 2020-07-14 | 华中科技大学 | Preparation method and application of two-dimensional carbon nanosheet |
| CN111774086A (en) * | 2020-07-11 | 2020-10-16 | 湘潭大学 | Preparation method and application of covalent organic framework material derived heteroatom co-doped carbon nanosheet nonmetal hydrogenation catalyst |
| CN112265977A (en) * | 2020-11-02 | 2021-01-26 | 福建师范大学 | Method for preparing porous hollow carbon material by etching |
| CN113209939A (en) * | 2021-05-17 | 2021-08-06 | 中国科学院青海盐湖研究所 | Metal sulfide-magnesium oxide-modified biomass charcoal composite material and preparation method and application thereof |
| CN113800518A (en) * | 2020-06-17 | 2021-12-17 | 厦门稀土材料研究所 | Nitrogen-doped high-specific-surface-area porous carbon material and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070202334A1 (en) * | 2005-12-29 | 2007-08-30 | Rong-Cai Xie | Nanoparticles containing titanium oxide |
| WO2014021257A1 (en) * | 2012-07-30 | 2014-02-06 | 国立大学法人信州大学 | Method for producing composite film comprising graphene and carbon nanotubes |
| US20160282721A1 (en) * | 2015-03-24 | 2016-09-29 | Samsung Electronics Co., Ltd. | Hardmask composition and method of forming pattern using the same |
| CN107032407A (en) * | 2017-04-10 | 2017-08-11 | 福州大学 | A kind of preparation method of novel porous carbon nanosheet |
| CN107082408A (en) * | 2017-06-22 | 2017-08-22 | 山东大学 | A kind of method that utilization freeze-drying process prepares porous boron carbon nitrogen nanometer sheet |
| CN108002374A (en) * | 2017-12-14 | 2018-05-08 | 合肥工业大学 | A kind of ultra-thin two-dimension stratified material nanometer sheet and preparation method thereof |
-
2018
- 2018-05-15 CN CN201810459486.3A patent/CN108529591B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070202334A1 (en) * | 2005-12-29 | 2007-08-30 | Rong-Cai Xie | Nanoparticles containing titanium oxide |
| WO2014021257A1 (en) * | 2012-07-30 | 2014-02-06 | 国立大学法人信州大学 | Method for producing composite film comprising graphene and carbon nanotubes |
| US20160282721A1 (en) * | 2015-03-24 | 2016-09-29 | Samsung Electronics Co., Ltd. | Hardmask composition and method of forming pattern using the same |
| CN107032407A (en) * | 2017-04-10 | 2017-08-11 | 福州大学 | A kind of preparation method of novel porous carbon nanosheet |
| CN107082408A (en) * | 2017-06-22 | 2017-08-22 | 山东大学 | A kind of method that utilization freeze-drying process prepares porous boron carbon nitrogen nanometer sheet |
| CN108002374A (en) * | 2017-12-14 | 2018-05-08 | 合肥工业大学 | A kind of ultra-thin two-dimension stratified material nanometer sheet and preparation method thereof |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109592665A (en) * | 2019-01-21 | 2019-04-09 | 兖矿集团有限公司 | A kind of preparation method of nanoporous carbon materials |
| CN109592665B (en) * | 2019-01-21 | 2022-05-17 | 兖矿集团有限公司 | Preparation method of nano-porous carbon material |
| CN110902678A (en) * | 2019-11-01 | 2020-03-24 | 宁夏大学 | Method for preparing sulfur-oxygen co-doped porous carbon based on paper |
| CN111410186A (en) * | 2020-03-16 | 2020-07-14 | 华中科技大学 | Preparation method and application of two-dimensional carbon nanosheet |
| CN113800518A (en) * | 2020-06-17 | 2021-12-17 | 厦门稀土材料研究所 | Nitrogen-doped high-specific-surface-area porous carbon material and preparation method and application thereof |
| CN113800518B (en) * | 2020-06-17 | 2022-12-09 | 厦门稀土材料研究所 | Nitrogen-doped high-specific-surface-area porous carbon material and preparation method and application thereof |
| CN111774086A (en) * | 2020-07-11 | 2020-10-16 | 湘潭大学 | Preparation method and application of covalent organic framework material derived heteroatom co-doped carbon nanosheet nonmetal hydrogenation catalyst |
| CN111774086B (en) * | 2020-07-11 | 2022-09-02 | 湘潭大学 | Preparation method and application of covalent organic framework material derived heteroatom co-doped carbon nanosheet nonmetal hydrogenation catalyst |
| CN112265977A (en) * | 2020-11-02 | 2021-01-26 | 福建师范大学 | Method for preparing porous hollow carbon material by etching |
| CN113209939A (en) * | 2021-05-17 | 2021-08-06 | 中国科学院青海盐湖研究所 | Metal sulfide-magnesium oxide-modified biomass charcoal composite material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108529591B (en) | 2019-11-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108529591B (en) | A kind of porous carbon nanosheet and its preparation method and application of B, N codope | |
| Cai et al. | Porous carbon derived from cashew nut husk biomass waste for high-performance supercapacitors | |
| Chen et al. | Synthesis of porous carbon spheres derived from lignin through a facile method for high performance supercapacitors | |
| Qiu et al. | Biochar-based carbons with hierarchical micro-meso-macro porosity for high rate and long cycle life supercapacitors | |
| Wang et al. | Nitrogen self-doped porous carbon with layered structure derived from porcine bladders for high-performance supercapacitors | |
| Yuan et al. | Synthesis of hierarchically porous MnO2/rice husks derived carbon composite as high-performance electrode material for supercapacitors | |
| He et al. | Application of biomass-derived flexible carbon cloth coated with MnO2 nanosheets in supercapacitors | |
| Sun et al. | Facile and green synthesis of 3D honeycomb-like N/S-codoped hierarchically porous carbon materials from bio-protic salt for flexible, temperature-resistant supercapacitors | |
| Seo et al. | Self-assembled bimetallic cobalt–manganese metal–organic framework as a highly efficient, robust electrode for asymmetric supercapacitors | |
| Wu et al. | Hierarchical zinc cobalt sulfide flowers grown on nickel foam as binder-free electrodes for high-performance asymmetric supercapacitors | |
| Cheng et al. | Preparation of high performance supercapacitor materials by fast pyrolysis of corn gluten meal waste | |
| Zeng et al. | Ultrafastly activated needle coke as electrode material for supercapacitors | |
| Liu et al. | Nitrogen/sulfur dual-doped sponge-like porous carbon materials derived from pomelo peel synthesized at comparatively low temperatures for superior-performance supercapacitors | |
| Hao et al. | Preparation of porous carbons from waste sugar residue for high performance electric double-layer capacitor | |
| Xin et al. | 3D flower-like NiCo2O4 electrode material prepared by a modified solvothermal method for supercapacitor | |
| CN101531360A (en) | Method for preparing mesoporous carbon material | |
| Wang et al. | Novel activated N-doped hollow microporous carbon nanospheres from pyrrole-based hyper-crosslinking polystyrene for supercapacitors | |
| Han et al. | Herbaceous biomass waste-derived activated carbons for supercapacitors | |
| CN105016337B (en) | A kind of absorbent charcoal material and preparation method thereof can be used for electrode of super capacitor | |
| Li et al. | Hierarchical sandwich NiFe layered double hydroxide/reduced graphene oxide for high energy density asymmetric supercapacitors | |
| Mo et al. | Hierarchical porous carbon with three dimensional nanonetwork from water hyacinth leaves for energy storage | |
| Wang et al. | Electrospinning CoS 2/carbon nanofibers with enhanced stability as electrode materials for supercapacitors | |
| Qi et al. | Preparation of carbon microspheres from lignin–urea–formaldehyde resin for application in high-performance supercapacitor | |
| Ji et al. | Coral-like interconnected porous carbon derived from phenolic resin/ammonium alginate composite for high-rate supercapacitor | |
| Anand et al. | Walnut shell derived N, S co-doped activated carbon for solid-state symmetry supercapacitor device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20191122 |