CN106006599B - A kind of P of high S contents, S, the synthetic method of the meso-porous carbon material of N codopes and its application - Google Patents
A kind of P of high S contents, S, the synthetic method of the meso-porous carbon material of N codopes and its application Download PDFInfo
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- CN106006599B CN106006599B CN201610311775.XA CN201610311775A CN106006599B CN 106006599 B CN106006599 B CN 106006599B CN 201610311775 A CN201610311775 A CN 201610311775A CN 106006599 B CN106006599 B CN 106006599B
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 50
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000010189 synthetic method Methods 0.000 title claims abstract description 17
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011592 zinc chloride Substances 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- RAIPHJJURHTUIC-UHFFFAOYSA-N 1,3-thiazol-2-amine Chemical class NC1=NC=CS1 RAIPHJJURHTUIC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims abstract description 10
- 235000019799 monosodium phosphate Nutrition 0.000 claims abstract description 10
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000010453 quartz Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 5
- 239000000446 fuel Substances 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 238000010828 elution Methods 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 16
- 238000002360 preparation method Methods 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 22
- 229910052799 carbon Inorganic materials 0.000 description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 239000000463 material Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 14
- 229910052698 phosphorus Inorganic materials 0.000 description 12
- 238000011056 performance test Methods 0.000 description 11
- 230000005540 biological transmission Effects 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000002427 irreversible effect Effects 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000004434 sulfur atom Chemical group 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000006245 Carbon black Super-P Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000010408 sweeping Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000005255 carburizing Methods 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000013404 process transfer Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101000949825 Homo sapiens Meiotic recombination protein DMC1/LIM15 homolog Proteins 0.000 description 1
- 101001046894 Homo sapiens Protein HID1 Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 102100022877 Protein HID1 Human genes 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000000970 chrono-amperometry Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000026683 transduction Effects 0.000 description 1
- 238000010361 transduction Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01—INORGANIC CHEMISTRY
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- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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- 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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- 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
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Abstract
The present invention relates to a kind of P of high S contents, S, the synthetic method of the meso-porous carbon material of N codopes and its applications.Preparation method is as follows：Using 2 aminothiazoles and sodium dihydrogen phosphate as raw material, ZnCl2For solvent and catalyst, it is placed on tube furnace high temperature carbonation step method and obtains the P of high S contents, S, the meso-porous carbon material SNPPC of N codopes, wherein 800 specific surface areas of SNPPC are up to 1122.46m2/ g, between 20 50nm, sulfur content is up to 12.58%, SNPPC 800 and illustrates excellent lithium electrical property, hydrogen reduction performance and performance of the supercapacitor compared to the SNPC of low S in aperture.In addition, this method is easy to operate, yield is higher, there is more wide application prospect.
Description
Technical field
The invention belongs to inorganic nano material and electrochemical technology fields, and in particular to a kind of P of high S contents, S, N are co-doped with
The synthetic method of miscellaneous meso-porous carbon material and its application.
Background technology
In recent years, due to porous carbon materials, in catalysis, energy storage, gas separation etc., widely potential application causes
Everybody interest.Them are mainly due to such as high specific surface area of unrivaled characteristic, chemical stability, adjustable
Pore structure and hetero atom modification.However, the activated centre that original porous carbon is anchored on surface due to lacking illustrates weaker electricity
Chemism.It, can be with for the various modifications of carbon frame or surface due to specific surface area solid and the adjustability of electronics
Enhancing absorption, diffusion and activation.Therefore, foreign atom is to carbon frame, it will changes the energy shown and activity, becomes enhancingization
Learn the flexibility strategy of activity.Since Jasinski reports the carbon material of N doping for the first time, everybody has begun concern doped carbon
Design and synthesis.The doping of N atoms due to odd electron configuration and electronegativity feature, effectively raises electronics distribution and electricity
Lotus spin densities are introduced on active site to neighbouring carbon.In addition to N atoms, S atom is also considered as an effective side
No matter spatially and electronically active method changes porous carbon performance, due to S outer layers bielectron pair and the atom larger compared to C, N half
Diameter.
Due to respective chemical property and matched electronic structure, S, the porous carbon materials of N codopes have caused huge
Big concern, it is most of that excellent performance is presented in fuel cell, lithium battery and capacitor.Now, S, N are adulterated porous
The synthesis of carbon material mainly includes carbonization and contains S, the presoma of N, biomass molecule and ionic liquid etc..Main problem is
Since the gasification and post processing of S cause S contents relatively low in the porous carbon materials of the S of synthesis, N doping.This can weaken S atom to more
The influence of the electronic structure and geometry of hole carbon, therefore N can be reduced, the synergistic action effect of S, therefore, limitation S atom is in frame
It is for raising S atom content in frame and its important.Previous research is mainly the structure-activity relationship of SNPC rather than simple
Synthetic method.Up to now, S content methods are improved also to be rarely reported.
Invention content
In view of the problems of the existing technology, the purpose of the present invention is to provide a kind of P, the S of high S contents, N codopes
The synthetic method of meso-porous carbon material and its application, it introduces NaH by high temperature cabonization2PO4S, N presomas, the S of acquisition, N, P
The porous carbon materials of codope have the SNPC of larger specific surface area and the high amount containing S, and the SNPC compared to low S illustrates excellent
Different lithium electrical property, hydrogen reduction performance and performance of the supercapacitor, and these differences can be attributed to due to high S contents raising
S, the synergistic effect of N.
A kind of P of high S contents, S, the synthetic method of the meso-porous carbon material of N codopes, it is characterised in that with 2- ammonia
Base thiazole and sodium dihydrogen phosphate are raw material, ZnCl2For catalysts and solvents, under nitrogen atmosphere, above-mentioned raw materials are put into tube furnace
The P of the middle high S contents of one-step synthesis method, S, the meso-porous carbon material of N codopes.
A kind of P of high S contents, S, the synthetic method of the meso-porous carbon material of N codopes, it is characterised in that specific step
It is rapid as follows：
1) using thiazolamine as N sources and S sources, sodium dihydrogen phosphate be P sources, manual mixing is uniform, and with zinc chloride shape
Into sandwich structure, place into quartz boat；
2) quartz boat that step 1) obtains is put into tube furnace, in N2800 DEG C are warming up to 5 DEG C/min under atmosphere, often
A temperature section keeps 2h, and one-step method obtains the P of high S contents, S, the meso-porous carbon material of N codopes；
3) quartz boat after step 2) reaction is taken out, by 35% salt acid elution of the product in quartz boat, removes chlorination
Zinc, then washed with deionized water and ethyl alcohol and remove hydrochloric acid, then product in vacuum drying chamber is dried, SNPPC- is obtained after dry
800。
A kind of P of high S contents, S, the synthetic method of the meso-porous carbon material of N codopes, it is characterised in that step 2)
Middle N2Flow velocity is 28-35ml/min, preferably 30ml/min.
A kind of P of high S contents, S, the synthetic method of the meso-porous carbon material of N codopes, it is characterised in that step 3)
Middle vacuum drying chamber temperature is 75-85 DEG C, drying time 2.5-3.5h.
A kind of P of high S contents, S, the synthetic method of the meso-porous carbon material of N codopes, it is characterised in that step 3)
Middle vacuum drying chamber temperature is 80 DEG C, drying time 3h.
A kind of P of high S contents, S, the synthetic method of the meso-porous carbon material of N codopes, it is characterised in that SNPPC-
In 800 products, S contents are up to 12.58%, and specific surface area reaches 1122.46m2/g。
The S of the high S contents, N, the application of the meso-porous carbon materials of P codopes as cathode of lithium battery catalyst.
The S of the high S contents, N, the application of the meso-porous carbon materials of P codopes as fuel cell oxygen reduction catalyst.
The S of the high S contents, N, the application of the meso-porous carbon materials of P codopes as ultracapacitor catalyst.
By using above-mentioned technology, compared with prior art, beneficial effects of the present invention are as follows：
A kind of novel, effective method of successful design of the present invention synthesizes the S of 4 kinds high S contents, N, P codopes it is mesoporous
Carbon material obtains high S contents by introducing sodium dihydrogen phosphate to the presoma thiazolamine high temperature carbonation step method containing S, N
SNPPC；Wherein SNPPC-800S contents are up to 12.58%, and specific surface area reaches 1122.46m2/g；High S contents are attributed to
Oxygen-containing functional group promotes the absorption to S in sodium dihydrogen phosphate, and the sodium during biphosphate is received has the formation of dopant material and urges
Change acts on.Compared with other SNPPC materials, SNPPC-800 have high lithium battery specific capacity, excellent high rate performance, more preferably
Long-range circulation ability, in addition to this, SNPPC-800 shows preferable ORR and performance of the supercapacitor.It is made through the present invention
A series of characterizations and performance test show that excellent performance is derived from the S of high S contents, the synergistic effect of N.Therefore, this research provides
One potential no metal ORR catalyst and lithium cell cathode material improve the possibility of this kind of material practical application.
Description of the drawings
Fig. 1 a are the scanning electron microscope (SEM) photograph of 1 micron of SNPPC-800；
Fig. 1 b are the transmission electron microscope picture of 100 nanometers of SNPPC-800；
Fig. 1 c are the transmission electron microscope picture of 20 nanometers of SNPPC-800；
Fig. 1 d are the transmission electron microscope picture of 5 nanometers of SNPPC-800；
Fig. 1 e are the X-ray energy spectrogram scanning area of SNPPC-800；
The X-ray energy spectrogram carbon that Fig. 1 f are SNPPC-800 is swept；
The X-ray energy spectrogram nitrogen that Fig. 1 g are SNPPC-800 is swept；
The X-ray energy spectrogram sulphur that Fig. 1 h are SNPPC-800 is swept；
The X-ray energy spectrogram phosphorus that Fig. 1 i are SNPPC-800 is swept；
Fig. 2 is the X-ray diffractogram of 4 kinds of difference SNPPC products；
Fig. 3 is the Raman x ray diffration pattern x of 4 kinds of difference SNPPC products；
Fig. 4 is the x-ray photoelectron spectroscopy wide range figure of 4 kinds of difference SNPPC products；
Fig. 5 is the N of 4 kinds of difference SNPPC products2Adsorption curve；
Fig. 6 is the graph of pore diameter distribution of 4 kinds of difference SNPPC products；
Fig. 7 is SNPPC-800 and SNPPC-700 in 100mA.g-1Cycle performance figure；
Fig. 8 is SNPPC-800 in 500mA.g-1Cycle performance figure；
Fig. 9 is SNPPC-800 in 1000mA.g-1Cycle performance figure；
Figure 10 is the high rate performance figure of SNPPC-800 and SNPPC-700；
Figure 11 all materials are in the linear voltammogram of 1600rpm；
Figure 12 is K-L line of all material in 0.365V；
Figure 13 is the electron number and current density of SNPPC-800, NPC-800 and business Pt/C (20% load capacity)；
The mithridatism that Figure 14 is SNPPC-800 and Pt/C (20% load capacity) is tested；
The ultracapacitor CV that Figure 15 is SNPPC-800 schemes；
Figure 16 is the ultracapacitor high rate performance figure of SNPPC-800；
Figure 17 is the ultracapacitor high rate performance figure of SNPPC-800, SNPPC-700 and SNPC-800；
Figure 18 is SNPPC-800 ultracapacitor cycle life figures.
Specific embodiment
Technical scheme of the present invention is described further with specific embodiment below, but protection scope of the present invention is unlimited
In this：
The preparation of 1 meso-porous carbon material SNPPC-800 of embodiment
Thiazolamine (0.1282g), sodium dihydrogen phosphate (0.1536g) are weighed, and manual mixing is uniform, later by 2-
Aminothiazole is placed on two layers of ZnCl2Among (each 0.1736g) material, in sandwich-like, then it is placed in quartz boat, is placed on tube furnace
In, each temperature section is warming up to 5 DEG C/min under N2 (speed 30ml/min) atmosphere and keeps 2h, black powder is obtained, uses
35% hydrochloric acid washes away remaining ZnCl2, washed 3 times with deionized water and ethyl alcohol, the dry 3h at 80 DEG C of vacuum drying chamber, finally
The N in tube furnace2Under (speed 30ml/min) atmosphere, 200 DEG C of holding 2h obtain the P of high S contents, S, N codopes it is mesoporous
Carbon material SNPPC-800, S content is up to 12.58%, and specific surface area reaches 1122.46m2/g。
The S of high S contents that the present invention obtains, N, the meso-porous carbon material of P codopes is as fuel cell oxygen reduction catalyst
Application, performance test methods are as follows：
Weigh the 5% nafion solution of the catalyst SNPPC-800,0.2ml of 2mg and the ethyl alcohol of 1.8ml in 10ml from
In heart pipe, ultrasonic disperse is uniform.The glass-carbon electrode of the 4mm aluminium oxide of 0.05/0.3mm is polished, is next rinsed with water dry
Only.The above-mentioned solution of 10 μ l is added dropwise on glass-carbon electrode, it is dry under infrared lamp.Cyclic voltammetry is from Shanghai
The CHI760E electrochemical workstations of occasion China, the test carry out in the electrolytic cell of three-electrode system, and Ag/AgCl is reference electrode,
Platinum electrode is to electrode, and glass-carbon electrode is working electrode, and electrolyte is 0.1M KOH, before testing O logical first230min makes
Electrolyte is in saturation oxygen condition, and surface sweeping rate is 10mVs-1, voltage range is -1.0 to 0.2V.Linear volt-ampere test be
It is carried out on CHI760E electrochemical workstations and RRDE-3A (ALS), surface sweeping rate is 10mVs-1, working electrode is the glass carbon of 4mm
Electrode, Ag/AgCl are reference electrode, and platinum electrode is to electrode, electrolyte 0.1MKOH, leads to O first before testing2
30min, for rotating speed from 400 to 2025rpm, the electrode difference between Ag/AgCl electrodes and RHE is 0.965V.
The S of high S contents that the present invention obtains, N, meso-porous carbon material the answering as cathode of lithium battery catalyst of P codopes
With performance test methods are as follows：
Under an argon atmosphere, the assembling of CR2025 buttons half-cell is completed in glove box.Active material, Kynoar
(PVDF), transduction agent (super-P) is with 75:15:15 ratio mixes in N-Methyl pyrrolidone, and above-mentioned mixed liquor is uniformly applied
Dry on the copper foil of a diameter of 12nm, tabletting obtains working electrode, and working electrode sample size is about 3mg (2-3mg.cm-2), lithium piece is as reference electrode and to electrode.The LiPF of 1M6/ (EC+DMC) (volume ratios 1:1) it is electrolyte, diaphragm is
Celgard(2300).Constant current charge-discharge test carries out charge-discharge performance test using certain current density to simulated battery, fills
Discharge test voltage range is 0.0-3.0V, uses the new Weir Electronics Co., Ltd. in secondary cell performance detecting system ＜ Shenzhen) it adopts
Collect its charging and discharging curve and capacity.Cyclic voltammetry sweep speed is 0.1mV/S, is 0.0-3.0V during voltage, uses
Instrument is CHI660D electrochemical workstations.Electrochemical impedance test electrochemical impedance test frequency is 0.01 to 105Hz, instrument
For CHI660D and Zahner Zenniwn electrochemical workstations.
The S of high S contents that the present invention obtains, N, meso-porous carbon material the answering as ultracapacitor catalyst of P codopes
With performance test methods are as follows：
Ultracapacitor is tested with three-electrode system, and Hg/HgO electrodes are as reference electrode.Platinum electrode conduct pair
Electrode, 6M KOH are as electrolyte.Working electrode by ethanol solution mix 80% active material, 15% super-P,
5% polytetrafluoroethylene (PTFE) binding agent is dried to obtain.Charge-discharge test, cyclic voltammetry and EIS tests are used and lithium battery is tested
Same instrument.
It can be seen that apparent SNPPC-800 sheets are stacked in Fig. 1, there is hierarchical porous structure, this explains
SNPPC-800 has 1235m2/ g surface areas.
The preparation of 2 meso-porous carbon material SNPPC-700 of embodiment
Weigh ZnCl2(0.8815g), thiazolamine (0.1282g), ZnCl2(0.8815g), by ZnCl22- amino thiophenes
Azoles is placed on two layers of ZnCl2It among material, in sandwich-like, then is placed in quartz boat, is placed on N in tube furnace2(30ml/min) atmosphere
Under with 5 DEG C/min be warming up to 700 DEG C, keep 8h, obtain black powder, remaining ZnCl is washed away with 35% hydrochloric acid2, spend from
Sub- water and ethyl alcohol are washed 5 times, the dry 3h at 80 DEG C of vacuum drying chamber, finally the N in tube furnace2Under (30ml/min) atmosphere, 200
DEG C keep 2h, obtain the meso-porous carbon material SNPPC-700 of final products S, N, P codope.
Catalytic oxygen reduction reaction performance test conditions are in the same manner as in Example 1.
The preparation of 3 meso-porous carbon material SNPPC-600 of embodiment
Weigh ZnCl2(0.8815g), thiazolamine (0.1282g), ZnCl2(0.8815g), by ZnCl22- amino thiophenes
Azoles is placed on two layers of ZnCl2It among material, in sandwich-like, then is placed in quartz boat, is placed on N in tube furnace2(30ml/min) atmosphere
Under with 5 DEG C/min be warming up to 600 DEG C, keep 8h, obtain black powder, remaining ZnCl is washed away with 35% hydrochloric acid2, spend from
Sub- water and ethyl alcohol are washed several times, the dry 3h at 80 DEG C of vacuum drying chamber, finally the N in tube furnace2Under (30ml/min) atmosphere,
200 DEG C of holding 2h, obtain the meso-porous carbon material SNPPC-600 of final products S, N, P codope.
Catalytic oxygen reduction reaction performance test conditions are in the same manner as in Example 1.
The preparation of 4 meso-porous carbon material SNPPC-500 of embodiment
Weigh ZnCl2(0.8815g), thiazolamine (0.1282g), ZnCl2(0.8815g), by ZnCl22- amino thiophenes
Azoles is placed on two layers of ZnCl2Among material, in sandwich-like, it is placed on N in tube furnace2It is heated up under (30ml/min) atmosphere with 5 DEG C/min
To 500 DEG C, 8h is kept, black powder is obtained, remaining ZnCl is washed away with 35% hydrochloric acid2, washed with deionized water and ethyl alcohol several
It is secondary, the dry 3h at 80 DEG C of vacuum drying chamber, the finally N in tube furnace2Under (30ml/min) atmosphere, 200 DEG C of holding 2h are obtained
The meso-porous carbon material SNPPC-500 of final products S, N, P codope.
Catalytic oxygen reduction reaction performance test conditions are in the same manner as in Example 1.
The 4 kinds of products and SNPPC-800 obtained to the present invention carry out elemental analysis and x-ray photoelectron spectrum analysis, knot
Fruit is as shown in table 1：
Table 1 SNPPC-500, SNPPC-600, the elemental analysis of SNPPC-700and SNPPC-800 and x-ray photoelectron
Compose result
As seen from Table 1,3.86% highest of S contents in SNPPC-800.
Comparative example：
Using commercialized 20%Pt/C as contrast sample, performance test methods are as follows：By 2mg Pt/C catalyst,
The ethyl alcohol of 1.8mL：The nafion solution of 200 μ L, ultrasonic disperse 30 minutes take 10 μ L to drop on platinum carbon electrode, then in air
Electrode is made in middle room temperature condition drying；Using the electrode as working electrode, using platinum plate electrode as to electrode, using Ag/AgCl as reference
The three-electrode system of electrode carries out linear scan test and RDE tests in the KOH solution of the 0.1mol/L of oxygen saturation, sweeps
Speed is retouched as 100mV/s.
In the attached drawing of the present invention, Fig. 4 is the x-ray photoelectron spectroscopy wide range figure of 4 kinds of difference SNPPC products；Fig. 5 for 4 kinds not
With the N of SNPPC products2Adsorption curve；Fig. 6 is the graph of pore diameter distribution of 4 kinds of difference SNPPC products；Fig. 7 for SNPPC-800 and
SNPPC-700 is in 100mA.g-1Cycle performance figure；Fig. 8 is SNPPC-800 and SNPPC-700 in 500mA.g-1Cyclicity
It can figure；Fig. 9 is SNPPC-800 and SNPPC-700 in 1000mA.g-1Cycle performance figure；Figure 10 is SNPPC-800 and SNPPC-
700 high rate performance figure；Figure 11 all materials are in the linear voltammogram of 1600rpm；Figure 12 is all material in 0.365V
K-L lines；Figure 13 is the electron number of SNPPC-800, SNPC-800, SNPPC-700 and business Pt/C (20% load capacity)；Figure 14 is
The mithridatism of SNPPC-800 and Pt/C (20% load capacity)；The ultracapacitor CV that Figure 15 is SNPPC-800 schemes；Figure 16 is
The ultracapacitor high rate performance figure of SNPPC-800；Figure 17 is the super capacitor of SNPPC-800, SNPPC-700 and SNPC-800
Device high rate performance figure；Figure 18 is SNPPC-800 ultracapacitor cycle life figures.
SNPPC-500, SNPPC-600, SNPPC-700 and SNPPC-800 and comparative example that the present invention is obtained
SNPC-800, business Pt/C (20% load capacity) do various structures and performance test, and result is aobvious referring to Fig. 1-Figure 18, Fig. 1 a
The apparent form for showing synthesized S, N, P doping carbon material is porous fold impalpable structure class graphene-structured；Fig. 1 b-i are shown
Show that C, N, S, P are uniformly distributed on the carbon material, there are one 002 crystal face that apparent graphite peaks correspond to graphite, tables at 26 ° by Fig. 2
Bright SNPPC has certain regular graphitization crystalline region, and as carbonization temperature increases, 43 ° that peak is significantly raised, and Fig. 3 is shown
Raman ID/IGThe S2p peaks being raised in the x-ray photoelectron spectroscopy of 1.45, Fig. 4 by 1.25 gradually increase the doping for showing that more S are unordered
Enter, Fig. 5 shows that specific surface area is up to 1235m2/g；Fig. 6 shows that aperture is distributed between 10-45nm.
SNPPC ORR concrete outcomes are shown in attached drawing 11-14,800 DEG C of roastings that the best sample of catalytic effect is provided for embodiment 1
The nitrogen-doped carbon material of burning, take-off potential are -0.11V, current density 2.1mA.cm-2, electrode process transfer electron number be
4；NPC-800 catalyst be embodiment 5 provide nitrogen-doped carbon material (rise a spike potential be -0.15V, current density is
1.2mA.cm-2, 2.2) electrode process transfer electron number is；
The SNPPC-800 that the present invention obtains embodiment 1 is used for the S of lithium battery, N, and the meso-porous carbon material of P codopes is answered
With when being used as cathode of lithium battery, performance test methods are as follows：
SNPPC-800 is attached in CR2025 batteries in glove box and is evaluated, and SNPPC-800, super-P, PVDF are with 70:
15:15 ratio is dispersed in nmp solution, 3mg on working electrode figure, and lithium foil is used for doing to electrode and reference electrode, the EC of 1M and
DMC1:1 LiPF6For electrolyte.
SNPPC-800 negative material first laps charge/discharge capacity is 1340.66 and 678.35mAhg-1(100mAg-1), library
Human relations efficiency 99%, 50 circle after capacity can reach 675.1mAhg-1, in 0.1,0.25,0.5, and 1mAg-1Under capacity difference
For 720.2,671.3,570.6, and 467.5mAhg-1, 630.5mAhg is returned to after 55 circles-1, have preferable cycle performance and
High rate performance, NPC-800 poor-performings.Concrete outcome is shown in attached drawing 11.
The foregoing is merely the section Examples of the present invention, are not used for limiting the present invention.In every case according to the content of present invention institute
The equivalent changes and modifications done, all for protection scope of the present invention within.
We characterize the porous structure of SNPPC with scanning electron microscope and transmission electron microscope.Fig. 1 a can be seen that SNPPC-800 has
There are hierarchical porous structure, about 2-5 μm of aperture.It is apparent abnormal that Fig. 1 b-1c low power transmission electron microscopes can be seen that SNPPC-800 has
Carbon-coating is around cavity structure, the porous carbon structure reported before similar.Fig. 1 d high powers transmission electron microscopes can see aperture 5-20nm's
Unformed mesoporous carbon structure.Fig. 1 e-i element caps can be seen that C, N, S, P and be evenly distributed on porous carbon skeleton.
Fig. 2 illustrates the XRD of SNPPC-500, SNPPC-600, SNPPC-700 and SNPPC-800, these materials are at 26 °
With 43 ° there are two apparent graphite peaks, corresponding to 002 crystal face and 100 crystal faces, as temperature increases, peak angle degree where 002 crystal face
It tapers into, shows to increase with temperature, carbon-coating spacing becomes larger.43 ° of peak gradually increases, and shows that 100 crystal faces stack more
Orderly.When temperature increases to 900 DEG C, we have obtained ZnS, and XRD is further demonstrated a bit, this is because high temperature organic molecule
Whole decompose.
Raman spectrum is further utilized to probe into the internal structure of SNPPC, 1330cm-1Corresponding to sp3Defect, 1585cm-1It is right
It should be in the sp in face2Carbon shakes.Fig. 3 can be seen that the increase with carburizing temperature, ID/IGFrom 1.17 gradually to 1.37,
The I of SNPPC-800D/IGMore than other samples, this shows to be introduced in SNPPC-800 due to the defects of high temperature is a large amount of.1 yuan of table
Element analysis (EA) tests the content of C, N, S of SNPPC.SNPPC-500 has highest 14.03% N content, however, simultaneously
Not every N is entered in lattice.The N content of SNPPC-600, SNPPC-700 and SNPPC-800 is respectively
12.63wt%, 6.94wt% and 8.17wt%.With temperature, DEG C raising, S contents increase to from 8.25wt% from 500 to 700
25.05wt%, SNPPC-800S content drop to 12.58%, this is because the vaporization of S of the fractional load on carbon frame.
ICP-OES can be seen that the P content of SNPPC-800 and SNPPC-700 is respectively 1.07wt% and 0.31%, SNPPC-500 and
SNPPC-600XPS and ICP-OES do not detect P, show that low temperature P cannot be doped in C framework.SNPPC-700 and
For the S contents of SNPPC-800 higher than other documents of report, this is attributed to the doping of P and phosphorus source.When by the use of triphenylphosphine as phosphorus source
When, SNPPC-800 only has 8.69% S.The difference of S contents is mainly due to oxygen-containing group in sodium dihydrogen phosphate and receives and can carry
The content of S in high SNPPC-800.
XPS illustrates the composition and chemical environment of each element in SNPPC.Fig. 4 XPS illustrate C1s peaks (284.5eV), O1s
Peak (532.5eV), N1s peaks (399.2eV) and visible S2p peaks (162.3eV).It is found that in SNPPC-700 and SNPPC-800
P2p (133.30eV) peak, however do not found in SNPPC-500 and SNPPC-600.The presence at O1s peaks is attributed in raw material
Oxygen in sodium dihydrogen phosphate and oxygen and water in the air of absorption.
N2Adsorption/desorption is used for studying the specific surface area and pore-size distribution of SNPPC.From fig. 5, it can be seen that SNPPC-500 and
SNPPC-600 samples are in P/P00.4 does not have hysteresis loop, and SNPPC-700 and SNPPC-800 has hysteresis loop, is typically to be situated between
Porous materials.SNPPC-500 and SNPPC-600 is the fragment for having accumulated cracking presoma, and orderly porous structure is in 700 Hes
800 DEG C of generations, PXRD and TGA demonstrate this result.By calculating BET specific surface area, SNNPC-500, SNNPC-600,
The specific surface area of SNNPC-700 and SNNPC-800 is respectively 48.93,569.92,712.4 and 1122.46m2/g.Fig. 6 can be seen
Go out, the BJH pore diameter ranges of SNPPC-800 are 20-50nm.As carburizing temperature increases, specific surface area gradually increases.Larger ratio
Surface area and wider pore-size distribution advantageously reduce energy barrier, improve substrate transmission.
Lithium cell cathode material is tested
SNPPC-800 and SNPPC-700 is attached in CR2025 batteries in glove box with three electrodes as cathode of lithium battery
System is evaluated, and all specific capacities are obtained according to active material.Fig. 7 illustrates 0.1A.g-1Lower lithium battery cycle performance,
SNPPC-800 negative material first laps charge/discharge capacity is 2475.89 and 1134.11mAhg-1, coulombic efficiency 45.81% returns
Because of the irreversible capacity caused by by SEI layers.Coulombic efficiency after SNPPC-800 50 is enclosed is 99.47%, shows higher storage
Lithium and de- lithium performance.After 50 circles, SNPPC-800 illustrates highest reversible capacity 977.68mA.h.g-1, NPC-800, SPC-
800, SNPC-800 and SNPPC-700 is respectively 346,386,630 and 855mA.h.g-1。
Further verify the long-range cycle cyclical stability under high current density.Fig. 8-9 shows that SNPPC-800 is in 500mA
g─1Under, 150 circle of cycle, capacity can still reach 799.15mA.h.g─1, 1000mA g─1Under, cycle 200 is enclosed, and capacity is
599.63mA.h.g─1.Even if showing SNPPC-800 at higher current densities, preferable cyclical stability can be still kept.S
Content plays a vital effect for the preferable lithium electrical properties of SNPPC-800.
Figure 10 is illustrated from 100 to 1000mA g-1High rate performance, corresponding irreversible capacity is respectively 0.10,
0.25,0.50,1.0A·g-1Under 1098.07,928.86,750.63 and 606.54mA.h.g─1.As current density is gradual
Increase.Irreversible capacity is gradually reduced the dynamics Controlling for being attributed to electro-chemical conversion.When current density returns to 0.1Ag-1,80
Irreversible capacity still reaches 1023.19mA.h g after circle─1.Reversible capacity is always better than SNPPC-700 (890.92mA.h.g─1) and SNPC-800 (630.5mA.h.g─1).
The preferable lithium battery capacities of SNPPC-800 are attributed to high S contents and larger specific surface area, three-dimensional SNPPC-
800 high specific surface areas and orderly channel provide a large amount of lithium ion storage and diffusion admittance.Compared to SNPC and forefathers
Report, the S contents of SNPPC-800 higher produce the defects of a large amount of, effective electronic effect are produced to neighbouring carbon,
Improve the absorption and transmission of lithium ion.Therefore, big specific surface area and N, S synergistic effect are for storage excellent SNPPC-800
Lithium performance plays an important role.
Fuel battery negative pole oxygen reduction reaction
In order to study the ORR of SNPPC activity, full of O20.1M KOH in three-electrode system in tested, sweep
Rate is retouched as 10mV.s-1.Figure 11 illustrates the RDE scan lines of different materials 1600rpm.SNPPC-800 no matter current density also
It is that take-off potential is better than 20wt%Pt/C and others SNPPC materials, this is attributed to doping and causes a large amount of active site.
We have obtained K-L lines (Figure 12) from the LSV lines of different potentials, these lines illustrate preferable linear relationship, imply that pair
O2First order kinetics react and same electron transfer number mesh.The K-L lines of SNPC-800 are higher than other SNPC samples and SPC-
800 and NPC-800 samples, and close to Pt/C.Based on K-L lines, Figure 13 can be seen that SNPPC-800, SNPPC-700, SNPC-
800 and Pt/C is respectively 3.5,4.3,4.1,4.2 (unit is J) in the 0.365V ORR electron numbers shifted, shows SNPPC-
800 and Pt/C ORR follow 4 electronics mechanism, this result is similar with the doping porous material reported before.In order to compare, Figure 11
RDE the and K-L lines of SNPPC-500, SNPPC-600 and SNPPC-700 are illustrated to Figure 12.
The life test of SNPPC-800 and Pt/C is obtained by chronoamperometry.In fig. 14, we survey under 0.365V
2000 circles are tried, SNPPC-800 illustrates the current density reserved of higher 96.08%, and Pt/C is after 2000 circles
Have lost 33.06%.Show that SNPPC-800 has the cyclical stability more than Pt/C.
Performance of the supercapacitor is tested
In order to study the performance of the supercapacitor of SNPPC-800, CV three electrode bodies first in a 6M KOH electrolyte
System is tested.Figure 15 illustrates SNPPC-800 from the CV under the different sweep speeds of 5to 100mV/s, works as sweep speed
From 5to 20mV s-1, we can see that CV is a similar rectangular configuration, show the presence of double layer capacitor.When sweeping
Rate is retouched from 50 to 100mV/s, it has been found that the deformation of rectangle, the presence of fake capacitance caused by being attributed to doping.And SNPPC-
700 compare with SNPC-800, and SNPPC-800 has maximum area, represents due to capacitance high caused by high S contents.
Figure 16 further illustrates the super electricity of SNPPC-800, SNPPC-700 and SNPC-800 under different current densities
Container charging and discharging curve.GCD results slightly and linearly have a deviation, corresponding to the porous carbon current response of N, S, P doping.From figure
17 can be seen that SNPC-800, SNPPC-700 and SNPPC-800 in 0.5A g-1Under specific capacity be respectively 142.3,202.5
And 227.5F.g-1, in 10A g-1Under specific capacity be respectively 96.25,141.25 and 160.0F g-1.Figure 18 is illustrated in 10A
g-1Under, the cyclical stability of 6000 circles.After 6,000 circles, specific capacity 160.29Fg-1, show excellent cyclical stability.
Claims (8)
1. a kind of P of high S contents, S, the synthetic method of the meso-porous carbon material of N codopes, it is characterised in that with thiazolamine and
Sodium dihydrogen phosphate is raw material, ZnCl2For catalysts and solvents, under nitrogen atmosphere, above-mentioned raw materials are put into one-step method in tube furnace
The P of high S contents, S are synthesized, the meso-porous carbon material of N codopes is as follows：
1）Using thiazolamine as N sources and S sources, sodium dihydrogen phosphate is P sources, and manual mixing is uniform, and forms three with zinc chloride
Mingzhi's structure, places into quartz boat；
2）By step 1）Obtained quartz boat is put into tube furnace, in N2800 DEG C are warming up to 5 DEG C/min under atmosphere, each temperature
Section keeps 2h, and one-step method obtains the P of high S contents, S, the meso-porous carbon material of N codopes, N2Flow velocity is 28-35 ml/min；
3）Take out step 2）Quartz boat after reaction by 35% salt acid elution of the product in quartz boat, removes zinc chloride, then
It is washed with deionized water and ethyl alcohol and removes hydrochloric acid, then product in vacuum drying chamber is dried, product SNPPC- is obtained after dry
800。
2. a kind of P of high S contents according to claim 1, S, the synthetic method of the meso-porous carbon material of N codopes is special
Sign is step 2）Middle N2Flow velocity is 30ml/min.
3. a kind of P of high S contents according to claim 1, S, the synthetic method of the meso-porous carbon material of N codopes is special
Sign is step 3）Middle vacuum drying chamber temperature is 75-85 DEG C, drying time 2.5-3.5h.
4. a kind of P of high S contents according to claim 1, S, the synthetic method of the meso-porous carbon material of N codopes is special
Sign is step 3）Middle vacuum drying chamber temperature is 80 DEG C, drying time 3h.
5. a kind of P of high S contents according to claim 1, S, the synthetic method of the meso-porous carbon material of N codopes is special
Sign is in SNPPC-800 products that S contents are up to 12.58%, and specific surface area reaches 1122.46m2/g。
6. a kind of P of high S contents according to claim 1, S, the meso-porous carbon material of N codopes are urged as cathode of lithium battery
The application of agent.
7. a kind of P of high S contents according to claim 1, S, the meso-porous carbon materials of N codopes as fuel cell oxygen also
The application of raw catalyst.
8. a kind of P of high S contents according to claim 1, S, the meso-porous carbon material of N codopes are urged as ultracapacitor
The application of agent.
Priority Applications (1)
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| US10693139B2 (en) * | 2016-08-12 | 2020-06-23 | Korea Advanced Institute Of Science And Technology | Carbonaceous structure and method for preparing the same, electrode material and catalyst including the carbonaceous structure, and energy storage device including the electrode material |
| CN106629723A (en) * | 2016-12-30 | 2017-05-10 | 扬州大学 | Biomass-based N, S and P-containing co-doped porous carbon and application thereof |
| CN107369833A (en) * | 2017-07-01 | 2017-11-21 | 中国科学院兰州化学物理研究所 | A kind of preparation method of network-like carbon negative pole material |
| CN107706403B (en) * | 2017-11-20 | 2020-09-25 | 中国科学院过程工程研究所 | Composite carbon material, modified electrode material prepared from same and lithium ion battery |
| CN108493424B (en) * | 2018-04-11 | 2020-11-03 | 中科锂电新能源有限公司 | Nitrogen, phosphorus and sulfur co-doped composite carbon material, preparation method thereof and lithium ion battery |
| CN109012749A (en) * | 2018-08-14 | 2018-12-18 | 青岛科技大学 | Nonmetallic difunctional VPO catalysts and its preparation method and application based on ZIF-8 phosphorus sulphur codope |
| CN110038638A (en) * | 2019-05-17 | 2019-07-23 | 浙江工业大学 | A kind of iron load nitrogen-doped porous carbon material and its synthetic method and application with excellent electro-catalysis reduction nitrogen performance |
| CN111082079B (en) * | 2019-12-30 | 2021-01-22 | 上海交通大学 | Bifunctional oxygen electrocatalyst material and preparation method and application thereof |
| CN114497593B (en) * | 2020-10-23 | 2024-04-02 | 中国石油化工股份有限公司 | Phosphorus-boron doped carbon material, platinum-carbon catalyst, and preparation methods and applications thereof |
| WO2023160592A1 (en) * | 2022-02-23 | 2023-08-31 | 中国石油化工股份有限公司 | Sulfur-containing platinum-carbon catalyst, preparation method therefor and use thereof |
| CN114715871B (en) * | 2022-04-26 | 2023-09-12 | 四川朗晟新材料科技有限公司 | Modified lithium iron phosphate positive electrode material for lithium battery and preparation method |
| CN116459857B (en) * | 2023-04-24 | 2024-04-19 | 安徽大学 | High-selectivity catalyst Co/NS800, preparation method thereof and method for selectively hydrogenating p-chloronitrobenzene in heterogeneous system |
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