CN106992076A - A kind of nitrogen, phosphorus, the preparation method of fluorin-doped carbon-based mixing capacitance material - Google Patents
A kind of nitrogen, phosphorus, the preparation method of fluorin-doped carbon-based mixing capacitance material Download PDFInfo
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- CN106992076A CN106992076A CN201710136476.1A CN201710136476A CN106992076A CN 106992076 A CN106992076 A CN 106992076A CN 201710136476 A CN201710136476 A CN 201710136476A CN 106992076 A CN106992076 A CN 106992076A
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- 239000000463 material Substances 0.000 title claims abstract description 61
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 23
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 21
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000011574 phosphorus Substances 0.000 title claims abstract description 17
- 238000002156 mixing Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 27
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 17
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011737 fluorine Substances 0.000 claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000003763 carbonization Methods 0.000 claims abstract description 6
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 239000000376 reactant Substances 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000005255 carburizing Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 5
- HJDKCHUESYFUMG-UHFFFAOYSA-N cycloocta-1,5-diene;nickel Chemical compound [Ni].C1CC=CCCC=C1 HJDKCHUESYFUMG-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000011435 rock Substances 0.000 claims description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000011144 upstream manufacturing Methods 0.000 claims description 4
- IPWBFGUBXWMIPR-UHFFFAOYSA-N 1-bromo-2-fluorobenzene Chemical compound FC1=CC=CC=C1Br IPWBFGUBXWMIPR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 239000003990 capacitor Substances 0.000 description 11
- 239000007772 electrode material Substances 0.000 description 7
- 239000003575 carbonaceous material Substances 0.000 description 5
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 3
- 235000011167 hydrochloric acid Nutrition 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
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- 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- 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
- H01G11/38—Carbon pastes or blends; Binders or additives therein
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
- Manufacturing & Machinery (AREA)
Abstract
A kind of nitrogen, phosphorus, the preparation method of fluorin-doped carbon-based mixing capacitance material, belong to the porous carbon-based capacitance material technical field of doping type.Carried out in anhydrous and oxygen-free inert environments, by catalyst and 2,2 ' bipyridyls are added in N, N ' dimethylformamides, add 1,5 cyclo-octadiene, are dissolved by heating；Nitrogen source and Fluorine source are added in solution, after heating response terminates, reactant taken out；Concentrated hydrochloric acid is added dropwise into resulting material, the colloidal solution doped with flocculent deposit is obtained；By material filtering, cleaning obtains the material containing N, F, the material containing N, F is transferred in porcelain boat, high temperature cabonization, and carburizing temperature scope is 500 1000 DEG C；Material after carbonization containing N, F and P sources are subjected to high temperature p-doped.Synthesis condition is gentle, and experimental implementation is simple, and the specific capacitance value of material is up to 250F g‑1, efficiently solve low and fake capacitance material circulation stability difference the problem of traditional Carbon-based supercapacitor energy density.
Description
Technical field
Invention belongs to the porous carbon-based capacitance material technical field of doping type, and in particular to one kind is porous using carbon containing, nitrogen, fluorine
Material is as presoma, and the method synthesis through two step high temperature cabonizations, fluorination, nitridation, phosphatization has electric double layer capacitance and counterfeit simultaneously
The mixed type capacitance material of capacitive property.
Background technology
Ultracapacitor is a kind of new type of energy storage device between battery and traditional capacitor, with cycle life
Long, the advantages of power density is high, charge/discharge rates are fast has broad application prospects.On electric automobile, ultracapacitor with
Battery joint can provide high power and high-energy respectively, not only reduced the volume of power supply but also extended the life-span of battery.Energy is close
Degree and power density are to weigh the leading indicator of performance of the supercapacitor, and the property of electrode material is to determine that capacitor energy is close
The key factor of the chemical properties such as degree, power density.In recent years, with the continuous expansion in supercapacitor applications field, surpass
The research of level capacitor electrode material is by the great attention of countries in the world, especially developed country.
Preferable electrode material should have higher specific capacitance, high rate capability and cyclical stability.Commercial at present
Super capacitor material is generally activated carbon, and the specific surface area of activated carbon is big and pore structure is adjustable, and then activated carbon only has double electricity
Layer capacitance, specific capacitance is still relatively low (generally in 120F g-1Left and right), so as to cause the energy density of super capacitor relatively low, therefore
Electrode material of the exploitation with excellent properties is problem most crucial during ultracapacitor is studied.
Fake capacitance capacitor is different from double layer capacitor, when fake capacitance electrode material is applied to capacitor, in electrode
Quick, reversible faraday's reaction redox reaction occurs for material surface, electric charge is shifted between the electrodes, result in method
Draw transmission of the electric current in super capacitor system.These electrochemistry Faradaic processes can not only expand the electricity of ultracapacitor
Scope is pressed, and the specific capacitance of ultracapacitor can be improved.Fake capacitance material can show more much bigger than electric double layer capacitance material
Specific capacitance and energy density.However, the power density of fake capacitance material is often below electric double layer capacitance material, and fake capacitance material
The cycle life of material is relatively low, it is impossible to meet use demand.Recent study personnel have found that the functional group of carbon material surface shows
Certain fake capacitance performance, but exploitation have concurrently simultaneously electric double layer capacitance and fake capacitance performance carbon material be still faced with it is very big
Challenge.
The content of the invention
The present invention has synthesized a kind of nitrogen, phosphorus, fluorin-doped porous carbon materials by simple method, and the material not only has
Electric double layer capacitance performance, also with fake capacitance performance, while having higher cycle life, solves traditional carbon-based super capacitor
Low and fake capacitance material circulation stability difference the problem of device energy density.
The present invention is achieved in the following ways：
Step 1) prepare the material containing N, F
The configuration of reaction mass is carried out in anhydrous and oxygen-free inert environments (glove box), by double (1, the 5- rings pungent two of catalyst
Alkene) nickel and 2,2 '-bipyridyl adds N, in N '-dimethyl formamide, adds 1,5- cyclo-octadiene, heating stirring has been allowed to
Fully dissolved；Nitrogen source and Fluorine source are added in solution afterwards, after reaction terminates, reactant is taken out for heating response；Catalyst and list
The molar ratio range of body (monomer refers to 2,2 '-bipyridyl, 1,5- cyclo-octadiene, nitrogen source and Fluorine source) is 2-6:1, preferably 4-6:
1, more preferably 5.2:1；Nitrogen source and Fluorine source consumption molar ratio range 0.5-2 in monomer:1, wherein it is preferred that 0.8-1.5：1, more preferably
1:1；It is 65-120 DEG C, more preferably preferably 75-100 DEG C, 85 DEG C to react heating-up temperature.Reaction time range is 7-20 hours, excellent
Select 8-12 hours, more preferably 10 hours；
Backward resulting material in be added dropwise concentrated hydrochloric acid, constantly rock, be changed into solution doped with the gluey molten of flocculent deposit
Liquid；Material is poured into bottle,suction filtering, and successively cleaned with chloroform, tetrahydrofuran and deionized water, the product of gained, is put into true
Dried under empty drying box；60-150 DEG C of vacuum drying temperature scope, more preferably preferably 80-120 DEG C, 100 DEG C.Drying time 8-24
Hour, preferably 10-15 hours, more preferably 12 hours.
Step 2) material containing N, F of synthesis is transferred in porcelain boat, and burning in high temperature process furnances is put into, in inert gas
In it is carbonized；Carburizing temperature scope is 500-1000 DEG C, preferably 800 DEG C -1000 DEG C.
Step 3) material containing N, F after carbonization is placed at porcelain boat downstream, P sources are placed on porcelain boat upstream end, and by porcelain boat
It is put into high temperature process furnances, high temperature p-doped under inert environments；P sources and step 2) in the mass ratio of material of synthesis be 1-15：1,
It is preferred that 3-8:1, more preferably 5:1,250-500 DEG C of phosphatization temperature, more preferably preferably 300-400 DEG C, 350 DEG C.
Nitrogen source preferably 2,4,6- tri- (4- bromophenyls) -1,3,5-triazines (TBT), Fluorine source preferably be selected from the bromo- 2- fluorobenzene of Isosorbide-5-Nitrae-two,
Bromo- 2, the 5- difluorobenzenes of Isosorbide-5-Nitrae-two, the preferred sodium hypophosphite of phosphorus source.Further preferably double (1,5- cyclo-octadiene) nickel and 2,2 '-connection pyrrole
The mol ratio of pyridine is 1:1；Double (1,5- cyclo-octadiene) nickel correspondence 0.505ml1,5- cyclo-octadiene per 1.125g.
Advantages of the present invention
It is of the invention that we have synthesized the porous carbon materials of N, P, F multi-element doping, synthesis condition temperature using easy method
Simple with, experimental implementation, the specific capacitance value of material is up to (250F g-1), efficiently solve traditional Carbon-based supercapacitor energy
Low and fake capacitance material circulation stability difference the problem of density, the design for high specific capacitance, long-life super capacitor material is provided
Basic guidance.It can ensure that carbon source in presoma, nitrogen source, Fluorine source, in the well mixed of molecular scale, pass through a step high temperature pyrolysis
Carbonization, nitridation, fluorination process are realized, and p-doped process is calcined by secondary high-temperature, nitrogen, phosphorus, fluorin-doped type is prepared many
Hole carbon material.The cost of material is low, easily prepared for this, not only with fake capacitance performance, also with electric double layer capacitance performance, follows simultaneously
Ring long lifespan.
Brief description of the drawings
The fluorin-doped porous carbon of nitrogen phosphorus of Fig. 1 embodiments 1 cyclic voltammetry curve in the case where difference sweeps speed；
Constant current charge-discharge curve of the fluorin-doped porous carbon of nitrogen phosphorus of Fig. 2 embodiments 1 under different current densities；
The fluorin-doped porous carbon of nitrogen phosphorus of Fig. 3 embodiments 1 is in 0.2A g-1Under charge and discharge cycles stability curve.
Specific embodiment mode
With reference to embodiment, the invention will be further described, but the present invention is not limited to following examples.
Embodiment 1
Step 1)：The configuration of reaction mass is carried out in glove box (anhydrous and oxygen-free inert environments), by catalyst 1.125g
(4.09mmol) double (1,5- cyclo-octadiene) nickel and 0.64g (4.09mmol) 2,2 '-bipyridyl are added to 60ml N, N '-diformazan
In base formamide, 0.505ml 1 is added, 5- cyclo-octadiene, 80 DEG C of heating stirrings are allowed to be completely dissolved.By 0.24g 2,4,
6- tri- (4- bromophenyls) -1,3,5-triazines (TBT) and the bromo- 2- fluorobenzene of 0.1g Isosorbide-5-Nitraes-two are added in above-mentioned solution, obtain purple
After reaction terminates, reactant is taken out for solution, 85 DEG C of heating responses 10 hours.5ml concentrated hydrochloric acids are added dropwise into taken material, no
It is disconnected to rock, it is changed into the green glue solution doped with light yellow flocculent deposit to solution.Material is poured into bottle,suction filtering, and first
Cleaned afterwards using 5 × 15mL chloroforms, 5 × 15mL tetrahydrofurans and 5 × 15mL deionized waters.The product of gained, is put into vacuum and does
Dried 12 hours at dry 100 DEG C of case.
Step 2)：The material containing N, F of synthesis is transferred in porcelain boat, and is put into 900 DEG C of burnings in high temperature process furnances, lazy
It is set to be carbonized in property gas.
Step 3)：The material containing N, F after carbonization is placed at porcelain boat downstream, sodium hypophosphite (Na2HPO2) is placed on porcelain boat
Upstream end, mass ratio is 1:5, and porcelain boat is put into high temperature process furnances, 350 DEG C of high temperature p-dopeds of inert environments.Final N is obtained,
The electrode material of P, F codope, the specific capacitance value of material is up to (250F g-1)。
Embodiment 2
Step 1)：The configuration of reaction mass is carried out in glove box (11.311 anhydrous and oxygen-free inert environments), by catalyst
Double (1, the 5- cyclo-octadiene) nickel of 1.125g (4.09mmol) and 0.64g (4.09mmol) 2,2 '-bipyridyl is added to 60ml N,
In N '-dimethyl formamide, 0.505ml 1 is added, 5- cyclo-octadiene, 80 DEG C of heating stirrings are allowed to be completely dissolved.
By 0.24g 2,4,6- tri- (4- bromophenyls) -1,3,5- triazines (TBT) and the bromo- 2,5- difluoros of 0.106g 1,4- bis-
Benzene is added in above-mentioned solution, obtains purple solution, 85 DEG C of heating responses 10 hours, and after reaction terminates, reactant is taken out.To
5ml concentrated hydrochloric acids are added dropwise in taken material, constantly rock, it is molten to be changed into green glue doped with light yellow flocculent deposit to solution
Liquid.Material is poured into bottle,suction filtering, and successively uses 5 × 15mL chloroforms, 5 × 15mL tetrahydrofurans and 5 × 15mL deionizations
Water is cleaned.The product of gained, is put at 100 DEG C of vacuum drying chamber and dries 12 hours.
Step 2)：The material containing N of synthesis is transferred in porcelain boat, and is put into 900 DEG C of burnings in high temperature process furnances, in inertia
It is set to be carbonized in gas.
Step 3)：The material containing N, F after carbonization is placed at porcelain boat downstream, sodium hypophosphite (Na2HPO2) is placed on porcelain boat
Upstream end, mass ratio is 1:5, and porcelain boat is put into high temperature process furnances, 350 DEG C of high temperature p-dopeds of inert environments.Obtain final N, P
The electrode material of codope.
Claims (10)
1. a kind of nitrogen, phosphorus, the preparation method of fluorin-doped carbon-based mixing capacitance material, it is characterised in that comprise the following steps：
Step 1) prepare the material containing N, F
The configuration of reaction mass is carried out in anhydrous and oxygen-free inert environments, by double (1, the 5- cyclo-octadiene) nickel and 2 of catalyst, 2 '-
Bipyridyl is added in N, N '-dimethyl formamide, adds 1,5- cyclo-octadiene, heating stirring is allowed to be completely dissolved；Afterwards will
Nitrogen source and Fluorine source are added in solution, and after reaction terminates, reactant is taken out for heating response；The mol ratio model of catalyst and monomer
Enclose for (2-6):1, monomer refers to 2,2 '-bipyridyl, 1,5- cyclo-octadiene, nitrogen source and Fluorine source；Nitrogen source and Fluorine source are used in monomer
Measure molar ratio range 0.5-2:1；It is 65-120 DEG C to react heating-up temperature；Reaction time range is 7-20 hours；
Backward resulting material in be added dropwise concentrated hydrochloric acid, constantly rock, the colloidal solution doped with flocculent deposit be changed into solution；Will
Material pours into bottle,suction filtering, and is successively cleaned with chloroform, tetrahydrofuran and deionized water, the product of gained, is put into vacuum and does
Dried under dry case；60-150 DEG C of vacuum drying temperature scope；Drying time 8-24 hour；
Step 2) material containing N, F of synthesis is transferred in porcelain boat, and burning in high temperature process furnances is put into, make in inert gas
It is carbonized；Carburizing temperature scope is 500-1000 DEG C；
Step 3) material containing N, F after carbonization is placed at porcelain boat downstream, P sources are placed on porcelain boat upstream end, and porcelain boat is put into
In high temperature process furnances, high temperature p-doped under inert environments；P sources and step 2) in the mass ratio of material of synthesis be 1-15：1, phosphatization
250-500 DEG C of temperature.
2. according to a kind of nitrogen described in claim 1, phosphorus, the fluorin-doped carbon-based preparation method for mixing capacitance material, its feature
It is, step 1) molar ratio range of catalyst and monomer is (4-6):1；Nitrogen source and Fluorine source consumption mol ratio 0.8-1.5：1；Instead
Answer 75-100 DEG C of heating-up temperature；Reaction time 8-12 hour；80-120 DEG C of vacuum drying temperature, drying time 10-15 hour.
3. according to a kind of nitrogen described in claim 1, phosphorus, the fluorin-doped carbon-based preparation method for mixing capacitance material, its feature
It is, step 1) mol ratio of catalyst and monomer is 5.2:1；Nitrogen source and Fluorine source consumption mol ratio 1:1；React heating-up temperature 85
℃；10 hours reaction time；100 DEG C of vacuum drying temperature, 12 hours drying times.
4. according to a kind of nitrogen described in claim 1, phosphorus, the fluorin-doped carbon-based preparation method for mixing capacitance material, its feature
It is, step 1).
5. according to a kind of nitrogen described in claim 1, phosphorus, the fluorin-doped carbon-based preparation method for mixing capacitance material, its feature
It is, step 1).
6. according to a kind of nitrogen described in claim 1, phosphorus, the fluorin-doped carbon-based preparation method for mixing capacitance material, its feature
It is, step 2) 800 DEG C -1000 DEG C of carburizing temperature.
7. according to a kind of nitrogen described in claim 1, phosphorus, the fluorin-doped carbon-based preparation method for mixing capacitance material, its feature
Be, step 3) in P sources and step 2) in the mass ratio of material of synthesis be 3-8:1；300-400 DEG C of phosphatization temperature.
8. according to a kind of nitrogen described in claim 1, phosphorus, the fluorin-doped carbon-based preparation method for mixing capacitance material, its feature
Be, step 3) P sources and step 2) in the mass ratio of material of synthesis be 5:1,350 DEG C of phosphatization temperature.
9. according to a kind of nitrogen described in claim 1, phosphorus, the fluorin-doped carbon-based preparation method for mixing capacitance material, its feature
It is, nitrogen source preferably 2,4,6- tri- (4- bromophenyls) -1,3,5-triazines (TBT), Fluorine source preferably is selected from the bromo- 2- fluorobenzene of Isosorbide-5-Nitrae-two, 1,
Bromo- 2, the 5- difluorobenzenes of 4- bis-, the preferred sodium hypophosphite of phosphorus source.
10. according to a kind of nitrogen described in claim 1, phosphorus, the fluorin-doped carbon-based preparation method for mixing capacitance material, its feature
It is, double (1,5- cyclo-octadiene) nickel and 2, the mol ratio of 2 '-bipyridyl is 1:1；Double (1,5- cyclo-octadiene) nickel per 1.125g
Correspondence 0.505ml1,5- cyclo-octadiene.
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| CN108002378A (en) * | 2017-11-30 | 2018-05-08 | 嘉兴学院 | A kind of preparation method of structure-reinforced nitrogen-phosphor codoping carbon tube bundle |
| CN108492996A (en) * | 2018-03-02 | 2018-09-04 | 东华大学 | A kind of preparation method of fluorine, nitrogen co-doped class graphene film layer material |
| CN110877910A (en) * | 2018-09-06 | 2020-03-13 | 天津大学 | Preparation method of fluorine-nitrogen double-doped activated carbon used as supercapacitor electrode |
| CN112687478A (en) * | 2020-12-15 | 2021-04-20 | 河南师范大学 | Preparation method of supercapacitor based on hierarchical-pore nitrogen-fluorine-doped carbon material working electrode |
| CN113816375A (en) * | 2021-10-20 | 2021-12-21 | 温州大学 | P-containing tripyridine ligand derived carbon material and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108002378A (en) * | 2017-11-30 | 2018-05-08 | 嘉兴学院 | A kind of preparation method of structure-reinforced nitrogen-phosphor codoping carbon tube bundle |
| CN108002378B (en) * | 2017-11-30 | 2020-11-13 | 嘉兴学院 | Preparation method of nitrogen-phosphorus co-doped carbon tube cluster with reinforced structure |
| CN108492996A (en) * | 2018-03-02 | 2018-09-04 | 东华大学 | A kind of preparation method of fluorine, nitrogen co-doped class graphene film layer material |
| CN110877910A (en) * | 2018-09-06 | 2020-03-13 | 天津大学 | Preparation method of fluorine-nitrogen double-doped activated carbon used as supercapacitor electrode |
| CN112687478A (en) * | 2020-12-15 | 2021-04-20 | 河南师范大学 | Preparation method of supercapacitor based on hierarchical-pore nitrogen-fluorine-doped carbon material working electrode |
| CN113816375A (en) * | 2021-10-20 | 2021-12-21 | 温州大学 | P-containing tripyridine ligand derived carbon material and application thereof |
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