CN115010118A - Nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene, and preparation method and application thereof - Google Patents
Nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene, and preparation method and application thereof Download PDFInfo
- Publication number
- CN115010118A CN115010118A CN202210627218.4A CN202210627218A CN115010118A CN 115010118 A CN115010118 A CN 115010118A CN 202210627218 A CN202210627218 A CN 202210627218A CN 115010118 A CN115010118 A CN 115010118A
- Authority
- CN
- China
- Prior art keywords
- macroporous
- graphene
- nitrogen
- hierarchical
- mesoporous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 100
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 92
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 52
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 36
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000011593 sulfur Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims description 17
- 239000010426 asphalt Substances 0.000 claims abstract description 23
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 14
- 239000006227 byproduct Substances 0.000 claims abstract description 6
- 239000007773 negative electrode material Substances 0.000 claims abstract description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 26
- -1 alkali metal salt Chemical class 0.000 claims description 22
- 239000012298 atmosphere Substances 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 239000011780 sodium chloride Substances 0.000 claims description 13
- 229910001415 sodium ion Inorganic materials 0.000 claims description 11
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 claims description 10
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 9
- 239000001103 potassium chloride Substances 0.000 claims description 9
- 229920000877 Melamine resin Polymers 0.000 claims description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 8
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 6
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 claims description 4
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 238000004523 catalytic cracking Methods 0.000 claims description 2
- 229960003638 dopamine Drugs 0.000 claims description 2
- 150000002469 indenes Chemical class 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims 2
- 150000001239 acenaphthenes Chemical class 0.000 claims 1
- 150000004946 bicyclic arenes Chemical class 0.000 claims 1
- 239000011294 coal tar pitch Substances 0.000 claims 1
- 150000002468 indanes Chemical class 0.000 claims 1
- 239000011302 mesophase pitch Substances 0.000 claims 1
- 239000011301 petroleum pitch Substances 0.000 claims 1
- 239000011295 pitch Substances 0.000 claims 1
- 235000011164 potassium chloride Nutrition 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 239000011734 sodium Substances 0.000 abstract description 8
- 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 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 229910052708 sodium Inorganic materials 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052744 lithium Inorganic materials 0.000 abstract description 5
- 229910002804 graphite Inorganic materials 0.000 abstract description 2
- 239000010439 graphite Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 27
- 238000012360 testing method Methods 0.000 description 10
- 239000011148 porous material Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000003917 TEM image Methods 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000002135 nanosheet Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative 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
- Y02E60/10—Energy storage using batteries
-
- 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
Abstract
The invention provides a method for preparing nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene by taking asphalt and petrochemical byproduct liquid heavy aromatic hydrocarbon as raw materials. The hierarchical macroporous/mesoporous graphene material has a mutually communicated macroporous structure formed by graphene sheets, and the graphene sheets are provided with macropores and mesoporous holes; the nitrogen doping content of the hierarchical macroporous/mesoporous graphene material can reach about 25% at most, and the doping content of sulfur element is about 1.0% under the condition of not adding an additional sulfur source. The nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene is applied to lithium ion batteries and sodium ionsWhen used as a negative electrode material of a sub-battery, the material is 1A g ‑1 When the current density is circulated to 500 circles and 1000 circles, the specific capacity can reach 1025.5mAh g ‑1 (about 3 times the theoretical specific capacity of the graphite negative electrode) and 256.5mAh g ‑1 And has good lithium and sodium storage performance.
Description
Technical Field
The invention belongs to the technical field of graphene preparation, and particularly relates to nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene as well as a preparation method and application thereof.
Background
Graphene, as a typical two-dimensional material, tends to agglomerate due to pi-pi stacking during the preparation process, resulting in the loss of its own unique properties. The two-dimensional graphene is constructed into a three-dimensional structure with good tissue and interconnection, and the macroporous/mesoporous structure is constructed, so that the characteristics of the layered structure of the graphene can be kept, the specific surface area is higher, and the material energy transportation and exchange are more orderly, so that the graphene is endowed with multiple functions. On the other hand, nitrogen and sulfur elements have multiple electrons outside atomic nuclei, so that the electronic structure of the graphene can be improved after the nitrogen and sulfur elements are doped into the graphene lattice, and more excellent electrochemical performance is provided. Therefore, the nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene has wide application prospects in the field of electrochemical energy storage.
However, due to the structural inertness and sp of the crystalline carbon lattice 2 The high strength of covalent bonds between hybridized carbon atoms makes the synthesis of such three-dimensionally graded porous graphene a challenge. Currently, various synthetic methods have been reported, including Chemical Vapor Deposition (CVD), chemical activation, and the like. However, these methods designed for specific applications, such as chemical methods, are often plagued by problems such as chemical contamination or structural deterioration of graphene, and CVD methods generally require complicated steps and relatively high costs.
Asphalt is used as a low-value byproduct in the fossil fuel processing process, contains rich polycyclic aromatic hydrocarbon, is easy to polymerize and aromatize in the heat treatment process, and the developed graphene material utilizing the characteristic is widely applied to the fields of energy storage, adsorption, catalysis and the like. However, due to the molten state and fluidity of the pitch itself, the carbon atoms produced by its pyrolysis tend to produce large-sized aggregates. Meanwhile, it is difficult to controllably synthesize a three-dimensional graphene material having a hierarchical porous structure during carbonization because of the characteristics of pitch itself. Therefore, how to rapidly prepare the nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene at low cost is a great challenge.
Disclosure of Invention
The invention aims to solve the technical problem of providing nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene and a preparation method thereof aiming at the defects in the prior art. The nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene has excellent lithium storage and sodium storage cycle and rate performance, the preparation method is low in cost, acid and alkali, strong oxidant, etching agent and the like do not need to be added, and large-scale synthesis is easy.
The technical scheme adopted by the invention for solving the problems is as follows:
the nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene is integrally in a honeycomb three-dimensional structure formed by stacking graphene sheets, and macropores and/or mesopores are distributed on the graphene sheets; the aperture size of the macropores on the honeycomb three-dimensional structure is 0.5-5 microns; the size of macropores distributed on the graphene sheet is 50-100 nanometers, and the size of mesopores is 2-50 nanometers.
According to the scheme, the specific surface area of the hierarchical macroporous/mesoporous graphene is 120-400m 2 g -1 (ii) a The content of nitrogen doped atoms in the hierarchical macroporous/mesoporous graphene is 12-25%, and the content of sulfur doped atoms in the hierarchical macroporous/mesoporous graphene is 0.4-1.5%.
The preparation method of the nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene comprises the following steps:
1) ultrasonically dispersing asphalt by using liquid aromatic hydrocarbon, adding a nitrogen source and alkali metal salt, uniformly grinding and drying; the melting temperature of the alkali metal salt is 600-1000 ℃;
2) calcining the product obtained in the step 1) in an air atmosphere, then calcining in a protective atmosphere, washing, and drying to obtain the nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene.
According to the scheme, the asphalt is selected from one or more of petroleum asphalt, coal tar asphalt, mesophase asphalt and the like; the nitrogen source is one or more of melamine, urea, thiourea, polyaniline, phenylenediamine, dopamine and the like.
According to the scheme, the liquid aromatic hydrocarbon is one or a mixture of more of monocyclic aromatic hydrocarbon, bicyclic aromatic hydrocarbon and the like. Further, the monocyclic aromatic hydrocarbon is selected from one or a mixture of more of alkylbenzene, tetrahydronaphthalene, indane and the like; the bicyclic aromatic hydrocarbon is one or a mixture of more of naphthalene, acenaphthene, acenaphthylene and the like.
According to the scheme, the liquid aromatic hydrocarbon can also adopt a byproduct heavy aromatic hydrocarbon mixture generated by petroleum catalytic cracking, and the components of the mixture comprise: monocyclic aromatic alkylbenzene, tetrahydronaphthalene, indane, indene, bicyclic aromatic naphthalene, acenaphthene, acenaphthylene, a small amount of tricyclic aromatic hydrocarbon and the like can be used for dispersing asphalt.
According to the scheme, the alkali metal salt is selected from one or more of sodium chloride, potassium carbonate, lithium chloride and the like; wherein the mass fraction of the sodium chloride is between 50 and 100 percent. In order to ensure that the melting temperature is proper, the mass fraction of sodium chloride is required to be ensured to be not less than 50%.
According to the scheme, in the step 1), as the asphalt is in a flowing state, part of impurities and part of components can be dissolved after liquid aromatic hydrocarbon is added, and the aim of drying is to evaporate the solvent so as to change the asphalt into a high-viscosity precursor. Drying conditions generally adopt an oven drying at 70-90 ℃.
According to the scheme, in the step 1), the proportion relation between the asphalt mass and the liquid aromatic hydrocarbon volume is 1 g: (10-30) mL; the mass ratio of the asphalt to the alkali metal salt is 1:10-1: 100; the mass ratio of the nitrogen source to the asphalt is 1:10-1: 1.
According to the scheme, in the step 2), under the atmosphere, the temperature is increased to 400 ℃ at the heating rate of 1-5 ℃/min, and the calcining time is 2-6 hours; under the protective atmosphere, the temperature is raised to the calcination temperature of 700-1100 ℃ at the temperature raising rate of 1-5 ℃/min, and the calcination time is 2-8 hours. Wherein, during the calcining treatment in the protective atmosphere, one or more of protective gases such as argon, nitrogen, hydrogen-argon mixed gas and the like are adopted.
The hierarchical macroporous/mesoporous graphene can be applied as a negative electrode material of a lithium ion battery and/or a sodium ion battery.
In the prior art, graphene is sp 2 The structure is stable, so extra etching agents such as hydrogen peroxide and the like are usually needed for preparing the mesoporous graphene, thereby increasing the process complexity and environmental pollution. Compared with the prior art, the invention has the following beneficial effects:
firstly, preparing graphene by a solid-phase catalytic conversion method, and calcining in air to obtain a graphene precursor with a rich pore structure by a two-step calcination technology to inhibit aggregation of a carbon precursor; and calcining in a protective atmosphere to realize atom oriented rearrangement at high temperature, thereby obtaining the high-quality sulfur-nitrogen-doped hierarchical macroporous-mesoporous graphene. The invention avoids using strong acid strong oxidant, and the like to realize the construction of the macroporous-mesoporous structure, greatly reduces the industrial preparation cost of the hierarchical porous graphene and the dependence on expensive equipment, and has great potential to be applied to large-scale production.
Secondly, the invention removes the low boiling point component in the asphalt by liquid arene, avoids using organic solvent such as toluene, carbon tetrachloride and the like, and reduces the cost; in addition, the raw material takes petrochemical by-product asphalt as a carbon source, and the used liquid arene can be directly replaced by petrochemical by-product heavy arene, so that the cost is low; in addition, acid and alkali, strong oxidant, etching agent and the like are not needed in the preparation process.
Thirdly, the sulfur and nitrogen doped hierarchical macroporous-mesoporous graphene is used as a lithium ion and/or sodium ion battery cathode material, a three-dimensional network structure of the sulfur and nitrogen doped hierarchical macroporous-mesoporous graphene can provide a rapid transfer path for electrons, and mesoporous/macroporous on the graphene nanosheet can provide an excellent diffusion channel for ions, so that the diffusion path of lithium ions and sodium ions is shortened, and the permeation of electrolyte is facilitated; in addition, the porous structure can effectively relieve the structural stress generated when ions are repeatedly embedded/removed in the charging and discharging processes of the battery, so that the structural integrity of the material is maintained.
Therefore, the method has the advantages of simple process, low cost, wide raw material source, high three-dimensional degree of the graphene product, controllability of nitrogen doping and the like, and has extremely high large-scale application potential.
Drawings
Fig. 1(a-b) is an SEM image of the hierarchical macroporous/mesoporous graphene synthesized in example 1; fig. 1(c-d) is a TEM image of the hierarchical macroporous/mesoporous graphene synthesized in example 1.
Fig. 2 is a graph of nitrogen adsorption-desorption curves of final samples obtained in examples 1-4.
FIG. 3 is an XRD pattern of the final samples obtained in examples 1 to 4 and comparative examples 1 and 2.
FIG. 4 is a Raman diagram of the final samples obtained in examples 1-4 and comparative examples 1, 2.
FIG. 5(a) is a test chart of the charge-discharge cycle of the lithium ion battery of the final sample obtained in examples 1 to 4; FIG. 5(b) is a plot showing the rate of lithium ion battery performance of the final samples obtained in examples 1-4.
FIG. 6(a) is a test chart of the charge-discharge cycle of the sodium ion battery of the final sample obtained in example 1; fig. 6(b) is a sodium ion battery rate test chart of the final sample obtained in example 1.
Fig. 7(a-b) is an SEM image of nitrogen-doped hierarchical macroporous/mesoporous graphene synthesized in comparative example 1; fig. 7(c-d) is a TEM image of the hierarchical macroporous/mesoporous graphene synthesized in comparative example 1.
Fig. 8(a-b) is an SEM image of nitrogen-doped hierarchical macroporous/mesoporous graphene synthesized in comparative example 2; fig. 8(c-d) is a TEM image of the hierarchical macroporous/mesoporous graphene synthesized in comparative example 2.
FIG. 9(a) is a test chart of charge-discharge cycles of a lithium ion battery of the final graphene sample obtained in comparative example 1-2; FIG. 9(b) is a test chart of the rate of lithium ion battery of the final sample obtained in comparative example 1-2.
FIG. 10(a) is a sodium ion battery charge-discharge cycle test chart of the final graphene sample obtained in comparative example 1-2; FIG. 10(b) is a test chart of the rate of sodium ion battery of the final sample obtained in comparative example-2.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the content of the present invention, but the present invention is not limited to the following examples.
Example 1
A preparation method of nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene comprises the following specific steps:
1) in the embodiment, the liquid aromatic hydrocarbon is taken from a certain petrochemical oil refining enterprise at home, and comprises the following specific components: adding 10mL of the liquid aromatic hydrocarbon into 1g of petroleum asphalt, and then ultrasonically dispersing for 20min at 100w ultrasonic power to obtain a mixture A, wherein the liquid aromatic hydrocarbon is monocyclic aromatic hydrocarbon (alkylbenzene (53.2%), indane or tetrahydronaphthalene (30.2%, indenes (5.3%)), bicyclic aromatic hydrocarbon (naphthalene (0.8%), acenaphthene (3.1%), acenaphthylene (3.6%)), and other impurities (3.8%);
then, mixing and grinding the mixture A, 20g of mixed salt of NaCl and KCl (the mass ratio of NaCl to KCl is 1:1) and 0.4g of melamine uniformly, and drying at 80 ℃ to remove volatile substances to obtain a mixture B for later use;
2) keeping the temperature of the mixture B at 360 ℃ for 4 hours in an air atmosphere, then slowly heating to 700 ℃ at the speed of 5 ℃/min in an argon atmosphere, and keeping the temperature for 2 hours; and cooling the product to room temperature, washing and drying to obtain the nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene.
As shown in fig. 1, the microstructure of the nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene prepared in example 1 is a three-dimensional honeycomb structure formed by graphene sheets and communicated with each other, and the pore size is 0.5-5 micrometers; as can be seen from fig. 1b, the graphene sheet is thin, and the nano-sheets have nano-holes with different sizes. The abundant macropore/mesopore structure on the graphene nanosheet can be clearly seen from the TEM image, the mesopore size is 2-50 nm, and the macropore size is 50-100 nm (c-d in FIG. 1).
As can be seen from fig. 2, the specific surface area of the nitrogen-and sulfur-doped hierarchical macroporous/mesoporous graphene prepared in example 1 is 267m 2 g -1 Pore size distribution 15,22,35,50,73,94nm (table 1), including mesoporous and macroporous structures.
The contents of nitrogen atom and sulfur atom in the nitrogen-doped and sulfur-doped hierarchical macroporous/mesoporous graphene obtained in example 1 were 12.2% and 1.3%, respectively, as detected by XPS (table 2).
The XRD pattern of the nitrogen-and sulfur-doped hierarchical macroporous/mesoporous graphene obtained in example 1 is shown in fig. 3, and the curve has two broad peaks corresponding to diffraction peaks of graphene on (002) plane and (100) plane, respectively.
FIG. 4 is a Raman diagram of the nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene obtained in example 1, wherein two Raman diagrams are observed at 1330cm -1 And 1591cm -1 Characteristic peaks in the vicinity corresponding to lattice defects and sp of carbon atoms, respectively 2 In-plane stretching vibration of hybridized carbon atoms; furthermore, at about 2800cm -1 The peak at (A) represents the 2D peak of graphene, which is formed by two phonon latticesThe effect of the vibration behaviour occurs.
Example 2
A preparation method of nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene comprises the following specific steps:
1) mixing alkylbenzene, tetrahydronaphthalene and acenaphthylene into 20mL in a volume ratio of 1:1:1, adding 1g of petroleum asphalt, and performing ultrasonic dispersion for 20min (ultrasonic power is 100w) to obtain a mixture A;
then, mixing and grinding the mixture A, 20g of mixed salt of NaCl and KCl (the mass ratio of the NaCl to the KCl is 1:1) and 0.8g of melamine uniformly, and drying at 80 ℃ to remove volatile substances to obtain a mixture B for later use;
2) keeping the temperature of the mixture B at 380 ℃ for 4 hours in an air atmosphere, then heating to 800 ℃ at the speed of 5 ℃/min in an argon atmosphere, and keeping the temperature for 2.5 hours; and cooling the product to room temperature, washing and drying to obtain the nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene.
Example 3
A preparation method of nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene comprises the following specific steps:
1) mixing alkylbenzene and indane in the same volume ratio of 1:1 to obtain 15mL, adding 1g of petroleum asphalt, and performing ultrasonic dispersion for 20min (the ultrasonic power is 100w) to obtain a mixture A;
then, mixing and grinding the mixture A, 20g of mixed salt of NaCl and KCl (the mass ratio of the NaCl to the KCl is 1:1) and 1.0g of melamine uniformly, and drying at 80 ℃ to remove volatile substances to obtain a mixture B for later use;
2) keeping the temperature of the mixture B at 400 ℃ for 4 hours in an air atmosphere, then slowly heating to 800 ℃ at the speed of 2 ℃/minute in a hydrogen argon atmosphere (wherein the volume fraction of hydrogen is 5 percent) and keeping the temperature for 4 hours; and cooling the product to room temperature, washing and drying to obtain the nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene.
Example 4
A preparation method of nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene comprises the following specific steps:
1) mixing 1g of petroleum asphalt with 10mL of alkylbenzene, and performing ultrasonic dispersion for 20min (the ultrasonic power is 100w) to obtain a mixture A;
then, mixing and grinding the mixture A, 20g of mixed salt of NaCl and KCl (the mass ratio of the NaCl to the KCl is 1:1) and 2.0g of melamine uniformly, and drying at 80 ℃ to remove volatile substances to obtain a mixture B for later use;
2) keeping the temperature of the mixture B at 400 ℃ for 4 hours in an air atmosphere, then heating to 1100 ℃ at the speed of 3 ℃/min in a nitrogen atmosphere, and keeping the temperature for 2 hours; and cooling the product to room temperature, washing and drying to obtain the nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene.
SEM, TEM, XRD and Raman of the nitrogen-and sulfur-doped hierarchical macroporous/mesoporous graphene prepared in examples 2 to 4 are similar to those of example 1, except that the nitrogen-and sulfur-doped hierarchical macroporous/mesoporous graphene samples obtained by different synthesis methods have different specific surface areas, and the pore size distributions are not completely the same, but have a macroporous/mesoporous structure as a common characteristic.
Comparative example 1
Comparative example 1 differs from example 1 only in that: in step 1), melamine and other nitrogen sources are not added.
As can be seen from the SEM images of fig. 7(a-b) and the TEM images of fig. 7(c-d), comparative example 1 has a microstructure similar to that of example 1, and exhibits an integrated porous network structure, and abundant mesopores exist on the surface and inside thereof.
In addition, the XRD, BET and Raman spectra of the sample of comparative example 1 were also determined to be similar to example 1 and are not listed here, except that XPS testing showed only 1.6% nitrogen content of the product, with small amounts of nitrogen and sulfur originating from the raw materials, as no additional nitrogen source was added.
Comparative example 2
Comparative example 2 differs from example 1 in that: in the step 1), melamine is not added; in step 2), the mixture B is kept at 360 ℃ for 4 hours in an argon atmosphere, and then heated to 700 ℃ at a rate of 5 ℃/min and kept at that temperature for 2 hours.
As can be seen from fig. 8(a-b), comparative example 2 was not subjected to air atmosphere heat treatment, and the sample was stacked with irregular lamellar structure graphene, and the whole had no significant three-dimensional pore structure. This is consistent with what is observed in the TEM image of FIG. 8 (c-d). From the nitrogen adsorption and desorption test, comparative example 2 has no obvious pore size distribution, which indicates that no macropores/mesopores exist in the prepared graphene sample (table 1).
Table 1 shows the specific surface area and pore size distribution data of examples 1-4 and comparative examples 1, 2 (note: the pore size in Table 1 is the pore size of the macropores/mesopores on the graphene nanoplatelets). Table 2 shows the data of the sulfur and nitrogen atom contents in XPS for examples 1-4 and comparative examples 1, 2.
TABLE 1
TABLE 2
As can be seen from Table 2, as the amount of the nitrogen source used was gradually increased in examples 2 to 4, it was demonstrated that the nitrogen doping concentration could be controlled by increasing the amount of the nitrogen source.
The application comprises the following steps: the materials of examples 1-4 were applied to Lithium Ion Battery (LIBs) and Sodium Ion Battery (SIBs) anode materials. The specific operation is as follows: the prepared graphene sample as an active material, a carbon black conductive agent and a PVDF adhesive are uniformly ground in a mortar in a mass ratio of 7:2:1 in advance, and then NMP is added for continuous grinding until uniform slurry is formed. The slurry was then knife coated onto copper foil with a doctor blade and dried in a vacuum oven at 120 ℃ for 12 hours, after which it was rolled and punched into circular pole pieces 12mm in diameter. And weighing and recording the mass of each pole piece in sequence, and multiplying the mass of the active substance, namely the mass difference between the pole piece mass and the blank copper foil wafer, by the proportion of the active substance. In a glove box (H) filled with argon 2 O<0.1ppm,O 2 <0.1ppm) was used in CR2025 button cell. The battery test system is adopted and is tested at 0.005-3V (vs. Li) by a Land CT2001A battery +/ Li) and 0.01-2.8V (vs. Na) + Na) was tested for constant current charge and discharge.
As shown in FIGS. 5 and 6, example 1 was used as negative electrodes of LIBs and SIBs at 1A g -1 When the current density is circulated to 500 circles and 1000 circles, the specific capacity is 1025.5mAh g -1 (about 3 times the theoretical specific capacity of the graphite negative electrode) and 256.5mAh g -1 And has excellent lithium and sodium storage cycle and rate performance.
Fig. 9 and 10 are performance graphs of lithium ion batteries and sodium ion batteries of the final graphene samples obtained in comparative example 1 and comparative example 2. Comparative example 1 as a negative electrode of LIBs, had a specific capacity of 789.3mAh g when cycled to 500 cycles -1 And at 5A g -1 The specific discharge capacity under a large current density is 315.6mAh g -1 . Comparative example 1 as negative electrode of SIBs at 1A g -1 When the current density of the lithium ion battery is cycled to 1000 circles, the specific discharge capacity of the lithium ion battery is 219.2mAh g -1 . Comparative example 1 has better lithium and sodium storage cycling and rate performance than comparative example 2 because comparative example 1 has a hierarchical macroporous/mesoporous structure that facilitates ion and electron transfer. But still lower than the lithium and sodium storage performance of example 1, mainly due to the following 2 points: firstly, the graphene three-dimensional network structure with the hierarchical porous structure can provide a rapid transfer path for electrons, and mesopores on the graphene nanosheets can provide excellent diffusion channels for ions, so that the diffusion path of lithium ions and sodium ions is shortened, and the electrolyte can be permeated conveniently; the porous structure can effectively relieve the structural stress generated when ions are repeatedly embedded/removed in the charging and discharging processes of the battery, so that the structural integrity of the material is maintained; on the other hand, the nitrogen doping enhances the intrinsic conductivity of the graphene, and is more beneficial to electron transmission, so that the energy storage performance is improved.
The raw materials listed in the invention, the upper and lower limits and interval values of the raw materials of the invention, and the upper and lower limits and interval values of the process parameters (such as temperature, time and the like) can all realize the invention, and the examples are not listed.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (10)
1. The nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene is characterized in that the whole graphene is a honeycomb three-dimensional structure formed by stacking graphene sheets, and macropores and/or mesopores are distributed on the graphene sheets; the aperture size of the macropores on the honeycomb three-dimensional structure is 0.5-5 microns; the size of macropores distributed on the graphene sheet is 50-100 nanometers, and the size of mesopores is 2-50 nanometers.
2. The N-doped hierarchical macroporous/mesoporous graphene as claimed in claim 1, wherein the specific surface area of the hierarchical macroporous/mesoporous graphene is 120-400m 2 g -1 (ii) a The content of nitrogen doped atoms in the hierarchical macroporous/mesoporous graphene is 12-25%, and the content of sulfur doped atoms in the hierarchical macroporous/mesoporous graphene is 0.4-1.5%.
3. A preparation method of nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene is characterized by comprising the following steps:
1) mixing asphalt and liquid aromatic hydrocarbon, performing ultrasonic dispersion, adding a nitrogen source and alkali metal salt, uniformly grinding and drying; the melting temperature of the alkali metal salt is 600-1000 ℃;
2) calcining the product obtained in the step 1) in an air atmosphere, then calcining in a protective atmosphere, washing, and drying to obtain the nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene.
4. The process according to claim 3, characterized in that in step 1), the ratio between the mass of bitumen and the volume of liquid aromatic hydrocarbon is 1 g: (10-30) mL; the mass ratio of the asphalt to the alkali metal salt is 1:10-1: 100; the mass ratio of the nitrogen source to the asphalt is 1:10-1: 1.
5. The preparation method according to claim 3, wherein the pitch is selected from one or more of petroleum pitch, coal tar pitch, and mesophase pitch; the nitrogen source is one or more of melamine, urea, thiourea, polyaniline, phenylenediamine and dopamine; the liquid aromatic hydrocarbon is one or a mixture of more of monocyclic aromatic hydrocarbon and bicyclic aromatic hydrocarbon.
6. The preparation method of claim 5, wherein the monocyclic aromatic hydrocarbon is selected from one or more of alkylbenzene, tetrahydronaphthalene and indane; the bicyclic arene is selected from one or a mixture of more of naphthalene, acenaphthene and acenaphthylene.
7. The method of claim 3, wherein the liquid aromatic hydrocarbon is a heavy aromatic hydrocarbon mixture produced as a byproduct of catalytic cracking of petroleum, and the composition comprises: monocyclic aromatic alkylbenzenes, tetrahydronaphthalenes, indanes, indenes, bicyclic aromatic naphthalenes, acenaphthenes, acenaphthylene, and small amounts of tricyclic aromatic hydrocarbons.
8. The method according to claim 3, wherein the alkali metal salt is selected from the group consisting of sodium chloride and one or more of potassium chloride, potassium carbonate, and lithium chloride; wherein the mass fraction of the sodium chloride is between 50 and 100 percent.
9. The method according to claim 3, wherein in the step 2), the calcination temperature is 300-400 ℃ and the calcination time is 2-6 hours under the atmospheric atmosphere; under the protective atmosphere, the calcining temperature is 700-1100 ℃, and the treatment time is 2-8 hours.
10. The use of the hierarchical macroporous/mesoporous graphene of claim 1 as a negative electrode material for a lithium ion battery and/or a sodium ion battery.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210627218.4A CN115010118B (en) | 2022-06-06 | 2022-06-06 | Nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210627218.4A CN115010118B (en) | 2022-06-06 | 2022-06-06 | Nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene and preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN115010118A true CN115010118A (en) | 2022-09-06 |
CN115010118B CN115010118B (en) | 2024-01-23 |
Family
ID=83072628
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210627218.4A Active CN115010118B (en) | 2022-06-06 | 2022-06-06 | Nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115010118B (en) |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130224603A1 (en) * | 2012-02-27 | 2013-08-29 | Guorong Chen | Lithium-ion cell having a high-capacity anode and a high-capacity cathode |
CN104495833A (en) * | 2015-01-14 | 2015-04-08 | 北京化工大学 | Three-dimensional structure sulfur-nitrogen codope hierarchical pore graphene and preparation method thereof |
CN105480971A (en) * | 2016-01-29 | 2016-04-13 | 福州大学 | Preparation method of asphalt-based three-dimensional mesoporous graphene material |
CN109626364A (en) * | 2019-01-29 | 2019-04-16 | 东北大学 | A kind of preparation method of nitrogen sulphur codope three-dimensional grapheme |
CN111039281A (en) * | 2019-12-26 | 2020-04-21 | 中国石油大学(华东) | Porous graphene material, preparation method thereof, capacitor electrode, capacitor and electric device |
CN112607733A (en) * | 2020-12-16 | 2021-04-06 | 董小珍 | Preparation method and application of polymer-based nitrogen and phosphorus doped graphitized porous carbon |
CN112758916A (en) * | 2020-12-25 | 2021-05-07 | 西安交通大学 | Active graphene and method for preparing active graphene through mesophase pitch |
CN113401894A (en) * | 2021-05-26 | 2021-09-17 | 武汉理工大学 | Method for preparing graphene by taking heavy aromatic hydrocarbon as raw material |
-
2022
- 2022-06-06 CN CN202210627218.4A patent/CN115010118B/en active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130224603A1 (en) * | 2012-02-27 | 2013-08-29 | Guorong Chen | Lithium-ion cell having a high-capacity anode and a high-capacity cathode |
CN104495833A (en) * | 2015-01-14 | 2015-04-08 | 北京化工大学 | Three-dimensional structure sulfur-nitrogen codope hierarchical pore graphene and preparation method thereof |
CN105480971A (en) * | 2016-01-29 | 2016-04-13 | 福州大学 | Preparation method of asphalt-based three-dimensional mesoporous graphene material |
CN109626364A (en) * | 2019-01-29 | 2019-04-16 | 东北大学 | A kind of preparation method of nitrogen sulphur codope three-dimensional grapheme |
CN111039281A (en) * | 2019-12-26 | 2020-04-21 | 中国石油大学(华东) | Porous graphene material, preparation method thereof, capacitor electrode, capacitor and electric device |
CN112607733A (en) * | 2020-12-16 | 2021-04-06 | 董小珍 | Preparation method and application of polymer-based nitrogen and phosphorus doped graphitized porous carbon |
CN112758916A (en) * | 2020-12-25 | 2021-05-07 | 西安交通大学 | Active graphene and method for preparing active graphene through mesophase pitch |
CN113401894A (en) * | 2021-05-26 | 2021-09-17 | 武汉理工大学 | Method for preparing graphene by taking heavy aromatic hydrocarbon as raw material |
Non-Patent Citations (2)
Title |
---|
LEI PAN等: "3D interconnected honeycomb-like and high rate performance porous carbons from petroleum asphalt for supercapacitors", APPLIED SURFACE SCIENCE, no. 444, pages 739 * |
本书编委会: "多孔材料 奇妙的微结构", 上海科学普及出版社, pages: 154 - 155 * |
Also Published As
Publication number | Publication date |
---|---|
CN115010118B (en) | 2024-01-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Li et al. | Hard carbon microtubes made from renewable cotton as high‐performance anode material for sodium‐ion batteries | |
Ju et al. | Few layer nitrogen-doped graphene with highly reversible potassium storage | |
Liu et al. | A waste biomass derived hard carbon as a high-performance anode material for sodium-ion batteries | |
Wang et al. | Conversion of diatomite to porous Si/C composites as promising anode materials for lithium-ion batteries | |
Zhao et al. | A universal method to fabricating porous carbon for Li-O2 battery | |
Park et al. | Enhancing the rate performance of graphite anodes through addition of natural graphite/carbon nanofibers in lithium-ion batteries | |
Fang et al. | Supercritical CO 2 mediated incorporation of sulfur into carbon matrix as cathode materials towards high-performance lithium–sulfur batteries | |
Luo et al. | Defect engineering of carbons for energy conversion and storage applications | |
Zuo et al. | Facile synthesis of three-dimensional porous carbon with high surface area by calcining metal–organic framework for lithium-ion batteries anode materials | |
Li et al. | Preparation of disordered carbon from rice husks for lithium-ion batteries | |
Ren et al. | Preparation of porous carbon microspheres anode materials from fine needle coke powders for lithium-ion batteries | |
Lin et al. | Synergistic engineering of cobalt selenide and biomass-derived S, N, P co-doped hierarchical porous carbon for modulation of stable Li-S batteries | |
Nie et al. | Hierarchical Porous Carbon Anode Materials Derived from Rice Husks with High Capacity and Long Cycling Stability for Sodium‐Ion Batteries | |
Qin et al. | Analogous graphite carbon sheets derived from corn stalks as high performance sodium-ion battery anodes | |
Wang et al. | Highly microporous graphite-like BC x O 3− x/C nanospheres for anode materials of lithium-ion batteries | |
Zhao et al. | Understanding the modulation effect and surface chemistry in a heteroatom incorporated graphene-like matrix toward high-rate lithium–sulfur batteries | |
Lin et al. | Superior performance asymmetric supercapacitors based on flake-like Co/Al hydrotalcite and graphene | |
Yang et al. | Polystyrene-derived carbon with hierarchical macro–meso–microporous structure for high-rate lithium-ion batteries application | |
Xu et al. | Hard carbon anodes derived from phenolic resin/sucrose cross‐linking network for high‐performance sodium‐ion batteries | |
Yi et al. | Nitrogen-rich graphene aerogel with interconnected thousand-layer pancake structure as anode for high performance of lithium-ion batteries | |
Zhu et al. | Three-dimensional porous graphene microsphere for high-performance anode of lithium ion batteries | |
Zhang et al. | A graphene/nitrogen-doped carbon nanofiber composite as an anode material for sodium-ion batteries | |
Gao et al. | Shape-controlled porous carbon from calcium citrate precursor and their intriguing application in lithium-ion batteries | |
Li et al. | Distinctive slit-shaped porous carbon encapsulating phosphorus as a promising anode material for lithium batteries | |
Guo et al. | Nitrogen-doped hierarchical porous carbon with ultrathin graphitic framework for superior lithium storage |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |