CN108584951A - The preparation method of nitrogen-phosphor codoping carbon electrode material with graded porous structure - Google Patents
The preparation method of nitrogen-phosphor codoping carbon electrode material with graded porous structure Download PDFInfo
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- CN108584951A CN108584951A CN201810682058.7A CN201810682058A CN108584951A CN 108584951 A CN108584951 A CN 108584951A CN 201810682058 A CN201810682058 A CN 201810682058A CN 108584951 A CN108584951 A CN 108584951A
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- phosphor codoping
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 76
- 239000007772 electrode material Substances 0.000 title claims abstract description 56
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 26
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 19
- 239000011574 phosphorus Substances 0.000 claims abstract description 18
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract description 11
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 11
- 239000008103 glucose Substances 0.000 claims abstract description 11
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 7
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 7
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 7
- 239000000467 phytic acid Substances 0.000 claims abstract description 7
- 229940068041 phytic acid Drugs 0.000 claims abstract description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012043 crude product Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- -1 nitrogen organic compound Chemical class 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 6
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 5
- 150000002894 organic compounds Chemical class 0.000 claims description 5
- 150000003233 pyrroles Chemical class 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- JXBAVRIYDKLCOE-UHFFFAOYSA-N [C].[P] Chemical group [C].[P] JXBAVRIYDKLCOE-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims 1
- 238000000967 suction filtration Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 33
- 239000003575 carbonaceous material Substances 0.000 abstract description 14
- 239000011148 porous material Substances 0.000 abstract description 7
- 239000007864 aqueous solution Substances 0.000 abstract description 5
- 230000004913 activation Effects 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 238000005255 carburizing Methods 0.000 abstract description 2
- 239000000470 constituent Substances 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 16
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 13
- 229910000019 calcium carbonate Inorganic materials 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 230000005611 electricity Effects 0.000 description 4
- 229920002239 polyacrylonitrile Polymers 0.000 description 4
- GZCGUPFRVQAUEE-VANKVMQKSA-N aldehydo-L-glucose Chemical compound OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)C=O GZCGUPFRVQAUEE-VANKVMQKSA-N 0.000 description 3
- 235000010216 calcium carbonate Nutrition 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000007974 melamines Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- 101100317222 Borrelia hermsii vsp3 gene Proteins 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/336—Preparation characterised by gaseous activating agents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
-
- 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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- 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)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention discloses the preparation methods of the nitrogen-phosphor codoping carbon electrode material with graded porous structure, using melamine cheap and easy to get etc. as carbon source, nitrogen source, phytic acid rich in phosphorus etc. is used as phosphorus source, two kinds of monomers react in the aqueous solution of glucose environment, a kind of nitrogenous carbon backbone structure with phosphorus of large size of sheet is formed, then uses nano-carbonate or bicarbonate as template, inlays between the layers, by the method for high temperature cabonization, it is made to release a large amount of CO2Carry out activation pore-creating, wherein remaining carbonate or oxide template are removed finally by dilute hydrochloric acid, carry out secondary pore-creating, obtaining one kind, there is a large amount of micropores and meso-hole structure, the nitrogen of high-specific surface area, the classifying porous carbon electrode material of phosphor codoping, the electrode material to have higher specific capacitance and good high rate performance in alkaline aqueous electrolyte.Change the dosage of carburizing temperature and carbonate template in carbon material miscellaneous constituent content and pore structure regulate and control, there is certain commercial value.
Description
Technical field
The invention belongs to electrode material technical fields, and in particular to one kind has the nitrogen-phosphor codoping carbon of graded porous structure
The preparation method of electrode material.
Background technology
Ultracapacitor is a kind of a kind of novel energy-storing element between conventional capacitor and chemical cell, relative to
For traditional plane-parallel capacitor, energy density is high, and for lithium ion battery, power density will be higher by more times, more
Gap between the two has been mended, its application range is made to be expanded significantly.Carbon-based supercapacitor is since its power density is high, peace
The advantages that complete reliable, service life is long, work warm limit for width and pollution is small, it is applicable to part second to a few minutes clock time
The application product for repeating electrical energy pulse becomes transport, regenerative resource, industry and consumer electronics and other application product
Preferred accumulation of energy and power transmission solution, such as in electric vehicle (EV/HEV), military project, light rail, aviation, electrical salf-walking
Vehicle, backup power supply, power generation (wind power generation, solar power generation), communication, consumption and the fields such as recreation electronic, signal monitoring electricity
Source application aspect has a vast market foreground.However, energy density (5~10Whkg of Carbon-based supercapacitor-1, only
1/20 or so of commercial Li-ion battery) it is relatively low, constrain its further development and application.Promote Carbon-based supercapacitor energy
One of key of metric density is to improve the capacitance of electrode material.Traditional carbon electrode material (includes mainly activated carbon, porous
Carbon, graphene etc.) capacitance almost entirely from electric double layer capacitance, pass through and increase carbon material specific surface area, regulation and control carbon material
The means such as pore structure (increasing micropore, structure grading-hole) can improve its capacitance to about 250Fg-1。
In the related technology, the capacitance of carbon material can be significantly improved by Heteroatom dopings such as N, P, B, S.Different is miscellaneous
There are notable differences for atom doped influence/castering action to carbon material physico-chemical property, capacitive property.N doping can improve carbon materials
The electric conductivity and hydrophily of material, and the fake capacitance that group containing N (such as pyridine N, pyrroles N) introduces can increase its capacitance；P is adulterated
A variety of P-O groups can be introduced, the hydrophily and stability of carbon material can be obviously improved, make carbon material that there is broader electrochemical window,
And also it is likely to provide certain fake capacitance.However, N doping can be such that the high rate performance of carbon material and cyclical stability becomes very
Difference；P adulterates the electric conductivity that can reduce material, can also reduce the specific surface area of material to a certain extent, make its capacity boost not
It is enough apparent.
Invention content
In view of this, having the embodiment provides one kind, energy density is high, good rate capability and cycle performance
The preparation method of the good classifying porous carbon electrode material of nitrogen-phosphor codoping.
In order to solve the above technical problems, technical solution used in the embodiment of the present invention is, the nitrogen with graded porous structure
The preparation method of phosphor codoping carbon electrode material, includes the following steps：
(1) it takes suitable carbon containing, nitrogen organic compound and glucose to be dissolved in the water, it is anti-that phosphorus-containing compound stirring is added
It answers；
(2) it after the completion of reacting, is added suitable nano-carbonate thereto or bicarbonate template is stirred to being uniformly dispersed,
It is filtered to obtain solid；
(3) obtained solid is placed in carbonization in the tube furnace of inert environments and obtains crude product；
(4) crude product is washed into removal carbonate or corresponding oxide obtains nitrogen-phosphor codoping graded porous carbon electricity
Pole material.
Preferably, in the step (1), carbon containing, nitrogen organic compound and the glucose stirring and dissolving at 20~80 DEG C；
Phosphorus-containing compound is added and is stirred to react 1~6h；The molar ratio of carbon containing, nitrogen the organic compound phosphorus-containing compound is 1:2~
1:6。
Preferably, in the step (1), carbon containing, nitrogen organic compound be melamine, dicyandiamide, urea, aniline,
One kind in pyrroles, polyacrylonitrile；The phosphorus-containing compound is one kind in phytic acid, phosphoric acid, triphenylphosphine.
Preferably, in the step (2), the carbonate or bicarbonate are sodium bicarbonate, saleratus or magnesium carbonate
In one kind.
Preferably, in the step (3), the temperature being carbonized in tube furnace is 700~1000 DEG C, and the time is 1~8h.
Compared with the relevant technologies, the advantageous effect that technical solution used in the embodiment of the present invention obtains is that the present invention is implemented
The preparation method of the nitrogen-phosphor codoping carbon electrode material with graded porous structure of example, is had using carbon containing, nitrogen cheap and easy to get
It machine compound and is reacted in aqueous solution with the compound rich in phosphorus, forms that a kind of large size of sheet is nitrogenous and the carbon skeleton of phosphorus
Then structure uses nano-carbonate or bicarbonate as template, inlay between the layers, by the method for high temperature cabonization,
It is set to release a large amount of CO2, activation pore-creating is carried out, wherein remaining carbonate or oxide mould are removed finally by dilute hydrochloric acid
Plate carries out secondary pore-creating, obtains a kind of having a large amount of micropores and meso-hole structure, the nitrogen of high-specific surface area, phosphor codoping classification more
Hole carbon electrode material, the electrode material have higher specific capacitance and good high rate performance in alkaline aqueous electrolyte.
1NPPC-850-M、1NPPC-1-850-M、1NPPC-2-850-M。
Description of the drawings
Fig. 1 is the carbon electrode material preparation method flow chart of the embodiment of the present invention；
Fig. 2 a are the SEM figures of 1NPPC-850-M prepared by the method for the embodiment of the present invention；
Fig. 2 b are the SEM figures of 1NPPC-850-M different resolutions prepared by the method for the embodiment of the present invention；
Fig. 2 c are the SEM figures of 1NPPC-0.5-850-M prepared by the method for the embodiment of the present invention；
Fig. 2 d are the SEM figures of 1NPPC-0.5-850-M different resolutions prepared by the method for the embodiment of the present invention；
Fig. 2 e are the SEM figures of 1NPPC-1-850-M prepared by the method for the embodiment of the present invention；
Fig. 2 f are the SEM figures of 1NPPC-1-850-M different resolutions prepared by the method for the embodiment of the present invention；
Fig. 3 is the nitrogen adsorption desorption figure of 1NPPC-1-850-M prepared by the method for the embodiment of the present invention；
Fig. 4 is the graph of pore diameter distribution of 1NPPC-1-850-M prepared by the method for the embodiment of the present invention；
Fig. 5 is the XRD diffracting spectrums of 1NPPC-1-850-M prepared by the method for the embodiment of the present invention；
Fig. 6 is 1NPPC-0.5-850-M, 1NPPC-1-850-M, 1NPPC-2- prepared by the method for the embodiment of the present invention
The CV comparison diagrams of 850-M；
Fig. 7 is 1NPPC-0.5-850-M, 1NPPC-1-850-M, 1NPPC-2- prepared by the method for the embodiment of the present invention
The high rate performance comparison diagram of 850-M；
Fig. 8 is 1NPPC-0.5-850-M, 1NPPC-1-850-M, 1NPPC-2- prepared by the method for the embodiment of the present invention
The impedance contrast collection of illustrative plates of 850-M；
Fig. 9 is 1NPPC1-850-M, 5NPPC-1-850-M, 10NPPC-1-850- prepared by the method for the embodiment of the present invention
The CV comparison diagrams of M；
Figure 10 is 1NPPC1-850-M, 5NPPC-1-850-M, 10NPPC-1- prepared by the method for the embodiment of the present invention
The high rate performance comparison diagram of 850-M；
Figure 11 is 1NPPC1-850-M, 5NPPC-1-850-M, 10NPPC-1- prepared by the method for the embodiment of the present invention
The impedance contrast collection of illustrative plates of 850-M；
Figure 12 is 1NPPC1-750-M, 5NPPC-1-800-M, 10NPPC-1- prepared by the method for the embodiment of the present invention
The CV comparison diagrams of 850-M；
Figure 13 is 1NPPC1-750-M, 5NPPC-1-800-M, 10NPPC-1- prepared by the method for the embodiment of the present invention
The high rate performance comparison diagram of 850-M；
Figure 14 is 1NPPC1-750-M, 5NPPC-1-800-M, 10NPPC-1- prepared by the method for the embodiment of the present invention
The impedance contrast collection of illustrative plates of 850-M.
Specific implementation mode
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached drawing to embodiment party of the present invention
Formula is further described.
Embodiment one
Referring to FIG. 1, the embodiment provides the nitrogen-phosphor codoping carbon electrode materials with graded porous structure
Preparation method, include the following steps：
(1) it takes suitable carbon containing, nitrogen organic compound and glucose to be dissolved in the water, it is anti-that phosphorus-containing compound stirring is added
It answers；The mass ratio of carbon containing, nitrogen organic compound and glucose is 20:1~2:1, the stirring and dissolving at 20~80 DEG C；Addition contains
Phosphorus compound is stirred to react 1~6h；The molar ratio of carbon containing, nitrogen the organic compound phosphorus-containing compound is 1:2~1:6；Contain
Carbon, nitrogen organic compound be melamine, dicyandiamide, urea, aniline, pyrroles, one kind in polyacrylonitrile, in aqueous solution
Meltage be 1g/250ml~1g/1000ml；The phosphorus-containing compound is one kind in phytic acid, phosphoric acid, triphenylphosphine；It chooses
Cost of material it is at low cost, and abundance；A kind of nitrogenous carbon with phosphorus of large size of sheet can be formed after the completion of being stirred to react
Skeleton structure；
(2) it after the completion of reacting, is added suitable nano-carbonate thereto or bicarbonate template is stirred to being uniformly dispersed,
It is filtered to obtain solid；Carbon containing, nitrogen the organic compound is 2 with the mass ratio of the carbonate or bicarbonate:1~
1:5；The carbonate or bicarbonate are one kind in sodium bicarbonate, saleratus or magnesium carbonate；Nano-carbonate or carbonic acid
Hydrogen salt is embedded in nitrogenous and phosphorus carbon backbone structure between layers；
(3) obtained solid is placed in the tube furnace of inert environments the pore-creating that is carbonized and obtains crude product；It is carbonized in tube furnace
Temperature be 700~1000 DEG C, the time be 1~8h；A large amount of CO is released during high temperature cabonization2Carry out activation pore-creating；
(4) crude product is washed into secondary pore-creating, vacuum drying obtains the classifying porous carbon electrode material of nitrogen-phosphor codoping,
Labeled as aNPPC-b-T-M (N/P co-doped Porous Carbon).It is removed in crude product by dilute hydrochloric acid or water washing
Carbonate or corresponding oxide process in realize secondary pore-creating；Wherein a indicates that the addition of glucose, b indicate carbonate
Addition, T indicate carburizing temperature；Last different letter represents different nitrogen sources, as follows respectively, M represent melamine,
D represents dicyandiamide, U represents urea, A represents aniline, Pyy represents pyrroles, PAN represents polyacrylonitrile.
The classifying porous carbon electrode material of nitrogen-phosphor codoping prepared by the embodiment of the present invention has a large amount of micropores and mesoporous knot
Structure, high-specific surface area；High rate performance and good cycling stability, capacitance are effectively promoted；And it can be by changing carbonization temperature
The dosage of degree and carbonate template in carbon material miscellaneous constituent content and pore structure regulate and control, it is commercialized to be that one kind is expected to
Carbon electrode material.
Embodiment two
According to embodiments of the present invention one method prepares the nitrogen-phosphor codoping carbon electrode material with graded porous structure, packet
Include following steps：
(1) glucose of 1.0g melamines and 47.2mg is taken to be dissolved in the water, phytic acid is added in the stirring and dissolving at 25 DEG C
And it is stirred to react 3h；
(2) after the completion of reacting, the Nano-meter CaCO3 of 0.5g is added thereto3Stirring is filtered and is consolidated to being uniformly dispersed
Body；
(3) obtained solid is placed in the tube furnace of nitrogen environment, is first warming up to 160 DEG C with 2 DEG C/min, it is pre- to be carbonized
6h, then sublevel section calcining first keep the temperature 1h, then keep the temperature 1.5h at 850 DEG C under the heating rate of 2 DEG C/min at 500 DEG C,
Crude product is obtained after being cooled to room temperature；
(4) crude product is washed for 24 hours with 2mol/L HCl, is then washed with deionized water to neutrality, the powder that will be obtained
End is dried in vacuo 12h at 60 DEG C and obtains the classifying porous carbon electrode material of nitrogen-phosphor codoping, is labeled as 1NPPC-0.5-850-M.
Remaining is the same as embodiment one.
It prepares according to the method for the embodiment of the present invention and does not add CaCO3, addition 1.0g CaCO3、2g CaCO3It prepares respectively
The carbon electrode material of nitrogen-phosphor codoping is obtained, 1NPPC-850-M, 1NPPC-1-850-M, 1NPPC-2-850-M are labeled as.
With reference to attached drawing 2a, 2b, 2c, 2d, 2e, 2f, 1NPPC-850-M carbon electrode materials only have the sheet in a small amount of accumulation hole
Structure；The surface of 1NPPC-0.5-850-M carbon electrode materials obviously can see the hole of 20 more~50nm, illustrate to be added
CaCO3With good pore-creating effect；The pore structure on 1NPPC-1-850-M carbon electrode materials surface is significantly more than 1NPPC-0.5-
850-M carbon electrode materials, show with CaCO3Increase, the pore structure on carbon electrode material surface is consequently increased.
With reference to attached drawing 3,4,1NPPC-850-M carbon electrode materials, 1NPPC-0.5-850-M carbon electrode materials, 1NPPC-1-
The specific surface area of 850-M carbon electrode materials is respectively 61.8m2/g、346.3m2/g、412.0m2/ g, shows with CaCO3For template,
The specific surface area of carbon material can be increased substantially, and by changing CaCO3Dosage, the specific surface area of material also changes,
And pore-size distribution also gap；Nitrogen adsorption desorption curve in figure is IV type, there is apparent hysteresis loop, is typical mesoporous material
Expect feature；While existing from can be seen that the existing micropore less than 2nm in material in graph of pore diameter distribution, and have 20~50nm left
Right mesoporous presence, and material has larger specific surface area, shows that carbon electrode material prepared by the embodiment of the present invention is a kind of
Carbon material with graded porous structure.
With reference to attached drawing 5, show that the classifying porous carbon electrode material of nitrogen-phosphor codoping prepared by the method for the embodiment of the present invention is
Apparent undefined structure is a kind of unformed classifying porous carbon material.
The preparation of electrode：The nickel sheet of the nickel foam of 1 × 2cm of clip and about 0.4 × 6cm, then weigh and (are repeated 4 times)；It presses
Mass ratio is 8：1：Slurry is made in 1 carbon electrode material, carbon black and the PTFE for weighing preparation of the embodiment of the present invention, wherein the present invention
The carbon electrode material 10mg of embodiment preparation, 6% PTFE aqueous solutions 20.8mg, carbon black 1.25mg, 5 electrodes of parallel making
Piece.
Specifically, weigh PTFE aqueous solutions 20.8mg in the small beaker of 5ml, then respectively weigh 1.25mg carbon black and
Carbon electrode material prepared by the embodiment of the present invention of 10mg is in small beaker, addition 5ml or so absolute ethyl alcohols, ultrasonic 30min, then
It is dried to obtain slurry；The slurry configured is coated onto in nickel foam and is pressed into electrode, claims its weight again after dry (at least 8h)
(being repeated 4 times)；Calculating difference obtains active material quality on electrode multiplied by with 0.8.1NPPC-850-M carbon electricity is prepared respectively
The electrode of pole material, the electrode of 1NPPC-0.5-850-M carbon electrode materials, 1NPPC-1-850-M carbon electrode materials electrode,
The electrode of 1NPPC-2-850-M carbon electrode materials.
The electrode of above-mentioned preparation is subjected to electro-chemical test, is carried out in VMP3 electrochemical workstations, using three electrode bodies
System, Pt electrodes are to electrode, and Hg/HgO electrodes are reference electrode, and 6mol/L KOH are electrolyte, after being completed, carry out CV
(cyclic voltammetric), GCD (constant current charge-discharge), EIS (impedance) tests.
With reference to attached drawing 6,7,8, have in the electrode CV curves of the carbon electrode material making of the method preparation of the embodiment of the present invention
Apparent redox peaks show to be successfully introduced into fake capacitance in material, that is, adulterate and have a positive effect to the capacitance promotion of material；
By high rate performance figure it is found that specific capacitances of the 1NPPC-1-850-M at 0.5A/g is 212.13F/g, when current density is increased to
When 20A/g, the capacitance retention of material is 74.92%, shows that material has good high rate performance, illustrate nitrogen-phosphor codoping,
There is actively impact to promoting the specific capacitance under high current density to doping type carbon material with graded porous structure.
Embodiment three
According to embodiments of the present invention one method prepares the nitrogen-phosphor codoping carbon electrode material with graded porous structure, packet
Include following steps：
(1) glucose of 1.0g melamines and 236mg is taken to be dissolved in the water, phytic acid is added in the stirring and dissolving at 25 DEG C
And it is stirred to react 3h；
(2) after the completion of reacting, the Nano-meter CaCO3 of 1.0g is added thereto3Stirring is filtered and is consolidated to being uniformly dispersed
Body；
(3) obtained solid is placed in the tube furnace of nitrogen environment, is first warming up to 160 DEG C with 2 DEG C/min, it is pre- to be carbonized
6h, then sublevel section calcining first keep the temperature 1h, then keep the temperature 1.5h at 850 DEG C under the heating rate of 2 DEG C/min at 500 DEG C,
Crude product is obtained after being cooled to room temperature；
(4) crude product is washed for 24 hours with 2mol/L HCl, is then washed with deionized water to neutrality, the powder that will be obtained
End is dried in vacuo 12h at 60 DEG C and obtains the classifying porous carbon electrode material of nitrogen-phosphor codoping, is labeled as 5NPPC-1-850-M.Its
Remaining same embodiment two.
It is more that the nitrogen-phosphor codoping classification that glucose dosage is 47.2mg and 472mg is prepared according to the method for the embodiment of the present invention
Hole carbon electrode material is respectively labeled as 1NPPC-1-850-M and 10NPPC-1-850-M.
Electrode is prepared according to the method for embodiment two and carries out electrode test.With reference to attached drawing 9,10,11, the embodiment of the present invention
Method prepare carbon electrode material make electrode CV curves in have apparent redox peaks, show to be successfully introduced into material
Fake capacitance, but with the increase of glucose dosage, redox peaks become smaller, can be seen that according to high rate performance figure, with grape
The increase of sugared dosage, capacitance retention reduce, and show that glucose dosage cannot be added excessively.
Example IV
According to embodiments of the present invention one method prepares the nitrogen-phosphor codoping carbon electrode material with graded porous structure, packet
Include following steps：
(1) glucose of 1.0g melamines and 47.2mg is taken to be dissolved in the water, phytic acid is added in the stirring and dissolving at 25 DEG C
And it is stirred to react 3h；
(2) after the completion of reacting, the Nano-meter CaCO3 of 1.0g is added thereto3Stirring is filtered and is consolidated to being uniformly dispersed
Body；
(3) obtained solid is placed in the tube furnace of nitrogen environment, is first warming up to 160 DEG C with 2 DEG C/min, it is pre- to be carbonized
6h, then sublevel section calcining first keep the temperature 1h, then keep the temperature 1.5h at 750 DEG C under the heating rate of 2 DEG C/min at 500 DEG C,
Crude product is obtained after being cooled to room temperature；
(4) crude product is washed for 24 hours with 2mol/L HCl, is then washed with deionized water to neutrality, the powder that will be obtained
End is dried in vacuo 12h at 60 DEG C and obtains the classifying porous carbon electrode material of nitrogen-phosphor codoping, is labeled as 1NPPC-1-750-M.Its
Remaining same embodiment two.
The nitrogen-phosphor codoping classification for preparing the heat preservation 1.5h at 800 DEG C and 850 DEG C according to the method for the embodiment of the present invention is more
Hole carbon electrode material is respectively labeled as 1NPPC-1-800-M, 1NPPC-1-850-M.
Electrode is prepared according to the method for embodiment two and carries out electrode test.Reference attached drawing 12,13,14,
There is apparent redox in the electrode CV curves that carbon electrode material prepared by the method for the embodiment of the present invention makes
Peak shows to be successfully introduced into fake capacitance in material, that is, adulterates and have a positive effect to the capacitance promotion of material, temperature is to introducing counterfeit electricity
The size of appearance is affected.
Herein, the nouns of locality such as involved front, rear, top, and bottom are to be located in figure with parts in attached drawing and zero
Part mutual position defines, only for the purpose of expressing the technical solution clearly and conveniently.It should be appreciated that the noun of locality
Use should not limit the claimed range of the application.
In the absence of conflict, the feature in embodiment and embodiment herein-above set forth can be combined with each other.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (7)
1. the preparation method of the nitrogen-phosphor codoping carbon electrode material with graded porous structure, characterized in that include the following steps：
(1) it takes suitable carbon containing, nitrogen organic compound and glucose to be dissolved in the water, phosphorus-containing compound is added and is stirred to react；
(2) after the completion of reacting, suitable nano-carbonate is added thereto or bicarbonate template is stirred to being uniformly dispersed, carries out
Suction filtration obtains solid；
(3) obtained solid is placed in the tube furnace of inert environments the pore-creating that is carbonized and obtains crude product；
(4) crude product is washed into secondary pore-creating and obtains the classifying porous carbon electrode material of nitrogen-phosphor codoping.
2. the preparation method of the nitrogen-phosphor codoping carbon electrode material according to claim 1 with graded porous structure,
It is characterized in, in the step (1), the mass ratio of carbon containing, nitrogen organic compound and glucose is 20:1~2:1,20~80
Stirring and dissolving at DEG C；Phosphorus-containing compound is added and is stirred to react 1~6h；Carbon containing, nitrogen the organic compound phosphorus-containing compound
Molar ratio is 1:2~1:6.
3. the preparation method of the nitrogen-phosphor codoping carbon electrode material according to claim 1 or 2 with graded porous structure,
It is characterized in that in the step (1), carbon containing, nitrogen organic compound is melamine, dicyandiamide, urea, aniline, pyrroles, gathers
One kind in acrylonitrile；The phosphorus-containing compound is one kind in phytic acid, phosphoric acid, triphenylphosphine.
4. the preparation method of the nitrogen-phosphor codoping carbon electrode material according to claim 1 with graded porous structure,
It is characterized in, in the step (2), the mass ratio of carbon containing, nitrogen the organic compound and the carbonate or bicarbonate is
2:1~1:5；The carbonate or bicarbonate are one kind in sodium bicarbonate, saleratus or magnesium carbonate；Nano-carbonate or
Bicarbonate stirring is embedded in nitrogenous and phosphorus carbon backbone structure between layers.
5. the preparation method of the nitrogen-phosphor codoping carbon electrode material according to claim 1 with graded porous structure,
It is characterized in, in the step (3), the temperature being carbonized in tube furnace is 700~1000 DEG C, and the time is 1~8h.
6. the preparation method of the nitrogen-phosphor codoping carbon electrode material according to claim 1 with graded porous structure,
It is characterized in, in the step (3), the temperature being carbonized in tube furnace is warming up to 160 DEG C with 2 DEG C/min, and be carbonized 6h in advance, then stage by stage
Calcining first keeps the temperature 1h, then keep the temperature 1.5h at 800 DEG C under the heating rate of 2 DEG C/min at 500 DEG C.
7. the preparation method of the nitrogen-phosphor codoping carbon electrode material according to claim 1 with graded porous structure,
Be characterized in, in the step (4), crude product uses dilute hydrochloric acid, water washing successively, clean be placed on it is dry in vacuum drying chamber
To the classifying porous carbon electrode material of nitrogen-phosphor codoping through secondary pore-creating.
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