CN112607733B - Preparation method and application of polymer-based nitrogen and phosphorus doped graphitized porous carbon - Google Patents
Preparation method and application of polymer-based nitrogen and phosphorus doped graphitized porous carbon Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 26
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 19
- 239000011574 phosphorus Substances 0.000 title claims abstract description 19
- 229920000642 polymer Polymers 0.000 title claims abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims description 7
- 239000000178 monomer Substances 0.000 claims abstract description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 9
- 229920001893 acrylonitrile styrene Polymers 0.000 claims abstract description 5
- 238000003763 carbonization Methods 0.000 claims abstract description 5
- 229920001577 copolymer Polymers 0.000 claims abstract description 5
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- YXVFYAGLYXEEHP-UHFFFAOYSA-N 2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane Chemical class O1CC2COP1OC2 YXVFYAGLYXEEHP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 239000012986 chain transfer agent Substances 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- YASRHLDAFCMIPB-UHFFFAOYSA-N (1-oxo-2,6,7-trioxa-1$l^{5}-phosphabicyclo[2.2.2]octan-4-yl)methanol Chemical compound C1OP2(=O)OCC1(CO)CO2 YASRHLDAFCMIPB-UHFFFAOYSA-N 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 6
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims 6
- 239000000203 mixture Substances 0.000 claims 3
- 239000003153 chemical reaction reagent Substances 0.000 claims 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000003999 initiator Substances 0.000 claims 1
- 239000012989 trithiocarbonate Substances 0.000 claims 1
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical compound [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 239000011148 porous material Substances 0.000 abstract description 8
- 125000003342 alkenyl group Chemical group 0.000 abstract description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 4
- 125000002743 phosphorus functional group Chemical group 0.000 abstract description 4
- AFINAILKDBCXMX-PBHICJAKSA-N (2s,3r)-2-amino-3-hydroxy-n-(4-octylphenyl)butanamide Chemical compound CCCCCCCCC1=CC=C(NC(=O)[C@@H](N)[C@@H](C)O)C=C1 AFINAILKDBCXMX-PBHICJAKSA-N 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 3
- 239000007789 gas Substances 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 239000010406 cathode material Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004966 Carbon aerogel Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- -1 acrylyl Chemical group 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- 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
- C01B32/20—Graphite
- C01B32/205—Preparation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
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- 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
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- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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
- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to the technical field of lithium ion batteries, and discloses a polymer nitrogen and phosphorus doped graphitized porous carbon, wherein a poly (acrylonitrile-styrene) copolymer of a phosphorus monomer is gasified and cracked in a pre-oxidation process, a large amount of gas is generated to escape from a matrix, a rich pore channel structure is left, a polyacrylonitrile thermosetting chain segment is crosslinked and solidified in a high-temperature carbonization process to form a carbon skeleton, and in the pre-oxidation process, a phosphorus group-containing alkenyl monomer is thermally cracked to generate a phosphoric acid derivative, so that the carbon skeleton has the function of catalyzing the carbon formation, the high-temperature carbonization process is accelerated, the carbon formation rate is improved, and the carbon skeleton is promoted to form compact and continuous graphitized porous carbon, so that the nitrogen and phosphorus doped graphitized porous carbon with rich pore structures and larger specific surface area is obtained, and the rich nitrogen-containing groups and phosphorus-containing groups improve the electrochemical properties, the pore structure and the specific surface area of the graphitized porous carbon.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method and application of polymer-based nitrogen and phosphorus doped graphitized porous carbon.
Background
The lithium ion battery has high energy density and stable cycle performance, is a green and environment-friendly secondary battery, the cathode material of the current commercial lithium ion battery is mainly graphite cathode material, but the theoretical specific capacity of graphite carbon is lower and is only 370mAh/g, the development and the application of the lithium ion battery are limited, the cathode material currently in hot spot research mainly comprises metal oxide electrode materials, metal alloy cathode materials, silicon-based cathode materials and carbon cathode materials, wherein the carbon cathode materials such as carbon aerogel, porous carbon, graphene, carbon nano tubes and the like have excellent electrochemical performance, and the cathode material is simple to prepare and wide in source, and is a lithium ion battery cathode material with great development potential.
The porous carbon has a large number of pore structures and ultrahigh specific surface area, and has rich sites for lithium removal and intercalation, and good electron conductivity and lithium ion diffusion coefficient, so that the novel porous carbon with excellent synthesis and development performances at present becomes a research hot spot to meet the application in the lithium ion battery anode material, wherein the heteroatom doping has the effects of adjusting the pore structure, specific surface area, electron arrangement and electrochemical property of the porous carbon by one of the most effective methods of doping nitrogen, sulfur, phosphorus and the like.
(one) solving the technical problems
Aiming at the defects of the prior art, the invention provides a preparation method and application of polymer-based nitrogen and phosphorus doped graphitized porous carbon, which have higher specific capacity and excellent multiplying power performance.
(II) technical scheme
In order to achieve the above purpose, the present invention provides the following technical solutions: the preparation method of the polymer-based nitrogen and phosphorus doped graphitized porous carbon comprises the following steps of:
(1) Adding dichloromethane solvent, 4-hydroxymethyl-1-oxo-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane and triethylamine into a reaction bottle, slowly dropwise adding acryloyl chloride at the temperature of between-10 and-0 ℃, uniformly stirring and reacting for 5-10 hours, distilling under reduced pressure to remove the solvent, washing with diethyl ether, adding methanol and distilled water, and recrystallizing and purifying to obtain the acrylated 1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane derivative.
(2) Adding N, N-dimethylformamide solvent, acrylonitrile, azodiisobutyronitrile and RAFT reagent in the mass ratio of 100:0.75-1.5:0.12-0.18 into a reaction bottle, placing the reaction bottle in an atmosphere reaction device, heating to 75-85 ℃ in a nitrogen atmosphere, reacting for 10-20h, vacuum drying to remove the solvent, washing with distilled water and methanol, and drying to obtain the polyacrylonitrile-based macromolecular chain transfer agent.
(3) Adding N, N-dimethylformamide solvent, styrene, acrylyl esterified 1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane derivative, polyacrylonitrile-based macromolecular chain transfer agent and initiator azodiisobutyronitrile into a reaction bottle, placing the mixture into an atmosphere reaction device, reacting for 12-24 hours at 80-90 ℃ under nitrogen atmosphere, vacuum drying to remove the solvent, washing with distilled water and methanol, and drying to obtain the poly (acrylonitrile-styrene) copolymer containing phosphorus monomer.
(4) And (3) placing the poly (acrylonitrile-styrene) copolymer containing the phosphorus monomer in an atmosphere furnace, and performing pre-oxidation and high-temperature carbonization treatment to prepare the polymer-based nitrogen-phosphorus doped graphitized porous carbon which is applied to the lithium ion battery anode material.
Preferably, the 4-hydroxymethyl-1-oxo-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] in step (1)]Octane of formula C 5 H 9 O 5 P, the structural formula isAcrylated 1-phospha-2, 6, 7-trioxabicyclo [2.2.2]Octane derivative of formula C 8 H 11 O 6 P is of the formula->
Preferably, the RAFT agent in step (2) is s, s '-bis (α, α' -dimethyl- α "-acetic acid) trithiocarbonate of formula C 9 H 14 O 4 S 3 The structural formula is
Preferably, the atmosphere reaction device in the step (2) comprises a heater, a water bath is arranged above the heater, a base is arranged inside the water bath, a clamping groove is fixedly connected to the upper side of the base, a pulley is movably connected to the clamping groove, the pulley is movably connected with a movable plate, a large reaction bottle and a small reaction bottle are arranged above the movable plate, a vent pipe is arranged above the water bath, and two ends of the vent pipe are respectively movably connected with an air inlet valve and an air outlet valve.
Preferably, the mass ratio of the styrene, the acrylated 1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane derivative, the polyacrylonitrile-based macromolecular chain transfer agent and the azodiisobutyronitrile in the step (3) is 100:20-40:8-15:0.1-0.2.
Preferably, the pre-oxidation treatment in the step (4) is an air atmosphere, and the pre-oxidation is performed for 3-6 hours at 220-280 ℃.
Preferably, the high-temperature carbonization treatment in the step (4) is performed in a nitrogen atmosphere at 750-800 ℃ for 2-3 hours.
(III) beneficial technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the polymer nitrogen and phosphorus doped graphitized porous carbon uses an acrylyl esterified 1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane derivative as an alkenyl monomer containing a phosphorus group, a polyacrylonitrile-based macromolecular chain transfer agent as a nitrogen-containing monomer, and polystyrene to be copolymerized by an efficient and controllable RAFT reversible addition-fragmentation chain transfer polymerization method to obtain a poly (acrylonitrile-styrene) copolymer of the phosphorus-containing monomer, so that nitrogen and phosphorus are controllable and highly distributed in a polymer molecular chain.
The polymer-based nitrogen and phosphorus doped graphitized porous carbon comprises a polystyrene thermoplastic chain segment and a polyacrylonitrile thermosetting chain segment in a molecular chain of a phosphorus monomer poly (acrylonitrile-styrene) copolymer, wherein the polystyrene thermoplastic chain segment is gasified and cracked in a pre-oxidation process to generate a large amount of gas which escapes from a matrix to leave a rich pore channel structure, the polyacrylonitrile thermosetting chain segment is crosslinked and solidified in a high-temperature carbonization process to form a carbon skeleton, in the pre-oxidation process, a phosphorus group-containing alkenyl monomer is thermally cracked to generate a phosphoric acid derivative, the phosphoric acid derivative has the function of catalyzing and carbonizing at a high temperature, the carbonizing process at a high temperature is accelerated, the carbonizing rate is improved, the carbon skeleton is promoted to form compact and continuous graphitized porous carbon, so that the graphitized porous carbon is rich in pore structure and larger in specific surface area, the electrochemical property, the pore structure and the specific surface area of the graphitized porous carbon are well promoted by rich nitrogen-containing groups, and the controllable nitrogen-containing porous carbon has the controllable and actual doping capacity of the graphitized porous carbon by controlling the alkenyl monomer containing the phosphorus groups and the amount of the polyacrylonitrile macromolecule chain transfer agent.
Drawings
FIG. 1 is a schematic view of an atmosphere reaction apparatus;
FIG. 2 is an enlarged schematic view of a base;
fig. 3 is a schematic diagram of the adjustment of the moving plate.
1-a heater; 2-a water bath kettle; 3-a base; 4-clamping grooves; 5-pulleys; 6-moving plate; 7-a large reaction bottle; 8-small reaction bottles; 9-a vent pipe; 10-an intake valve; 11-air outlet valve.
Detailed Description
In order to achieve the above object, the present invention provides the following specific embodiments and examples: the preparation method of the polymer-based nitrogen and phosphorus doped graphitized porous carbon comprises the following steps:
(1) Adding dichloromethane solvent with molecular formula of C into a reaction bottle 5 H 9 O 5 4-hydroxymethyl-1-oxo-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] P]Slowly dropwise adding acryloyl chloride into octane and triethylamine at the temperature of between-10 and-0 ℃ at the mass ratio of 170-190:110-120:100, uniformly stirring and reacting for 5-10h, distilling under reduced pressure to remove solvent, washing with diethyl ether, adding methanol and distilled water, and recrystallizing and purifying to obtain the molecular formula C 8 H 11 O 6 Acrylated 1-phospha-2, 6, 7-trioxabicyclo [2.2.2]An octane derivative.
(2) Adding N, N-dimethylformamide solvent into a reaction bottleAcrylonitrile, azobisisobutyronitrile and the molecular formula C with the mass ratio of 100:0.75-1.5:0.12-0.18 9 H 14 O 4 S 3 The RAFT reagent s, s ' -di (alpha, alpha ' -dimethyl-alpha ' -acetic acid) trithiocarbonate is placed in an atmosphere reaction device, the atmosphere reaction device comprises a heater, a water bath kettle is arranged above the heater, a base is arranged inside the water bath kettle, a clamping groove is fixedly connected above the base, a pulley is movably connected with a movable plate, a large reaction bottle and a small reaction bottle are arranged above the movable plate, a vent pipe is arranged above the water bath kettle, two ends of the vent pipe are respectively and movably connected with an air inlet valve and an air outlet valve, the temperature is heated to 75-85 ℃ under the nitrogen atmosphere, the reaction is carried out for 10-20 hours, the solvent is removed by vacuum drying, and the polyacrylonitrile-based macromolecular chain transfer agent is prepared by washing and drying with distilled water and methanol.
(3) Adding N, N-dimethylformamide solvent, styrene, acrylyl esterified 1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane derivative, polyacrylonitrile-based macromolecular chain transfer agent and initiator azodiisobutyronitrile into a reaction bottle, placing the mixture into an atmosphere reaction device, reacting for 12-24h at 80-90 ℃ under nitrogen atmosphere, vacuum drying to remove the solvent, washing with distilled water and methanol, and drying to obtain the poly (acrylonitrile-styrene) copolymer of the phosphorus-containing monomer.
(4) The preparation method comprises the steps of placing a poly (acrylonitrile-styrene) copolymer of a phosphorus-containing monomer in an atmosphere furnace, pre-oxidizing the poly (acrylonitrile-styrene) copolymer for 3-6 hours at 220-280 ℃ in an air atmosphere, heating the poly (acrylonitrile-styrene) copolymer to 750-800 ℃ and carbonizing the poly (acrylonitrile-styrene) copolymer for 2-3 hours at high temperature to prepare the polymer-based nitrogen-phosphorus doped graphitized porous carbon, and applying the polymer-based nitrogen-phosphorus doped graphitized porous carbon to a lithium ion battery anode material.
Example 1
(1) Adding dichloromethane solvent with molecular formula of C into a reaction bottle 5 H 9 O 5 4-hydroxymethyl-1-oxo-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] P]Slowly dropwise adding acryloyl chloride into octane and triethylamine at the temperature of 0 ℃ in a mass ratio of 170:110:100, uniformly stirring and reacting for 5 hours, distilling under reduced pressure to remove a solvent, washing with diethyl ether, adding methanol and distilled water, and recrystallizing and purifying to obtain the finished productTo formula C 8 H 11 O 6 Acrylated 1-phospha-2, 6, 7-trioxabicyclo [2.2.2]An octane derivative.
(2) Adding N, N-dimethylformamide solvent, acrylonitrile, azodiisobutyronitrile and the molecular formula C in a mass ratio of 100:0.75:0.12 into a reaction bottle 9 H 14 O 4 S 3 The RAFT reagent s, s ' -di (alpha, alpha ' -dimethyl-alpha ' -acetic acid) trithiocarbonate is placed in an atmosphere reaction device, the atmosphere reaction device comprises a heater, a water bath kettle is arranged above the heater, a base is arranged inside the water bath kettle, a clamping groove is fixedly connected above the base, a pulley is movably connected with a movable plate, a large reaction bottle and a small reaction bottle are arranged above the movable plate, a vent pipe is arranged above the water bath kettle, two ends of the vent pipe are movably connected with an air inlet valve and an air outlet valve respectively, the air inlet valve and the air outlet valve are heated to 75 ℃ under the nitrogen atmosphere to react for 10 hours, the solvent is removed by vacuum drying, and the polyacrylonitrile-based macromolecular chain transfer agent is prepared by washing and drying distilled water and methanol.
(3) Adding N, N-dimethylformamide solvent, styrene, acrylated 1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane derivative, polyacrylonitrile-based macromolecular chain transfer agent and initiator azodiisobutyronitrile into a reaction bottle, placing the mixture into an atmosphere reaction device, reacting for 12 hours at 80 ℃, drying in vacuum to remove the solvent, washing with distilled water and methanol, and drying to obtain the phosphorus-containing monomer poly (acrylonitrile-styrene) copolymer.
(4) And (3) placing the poly (acrylonitrile-styrene) copolymer of the phosphorus-containing monomer in an atmosphere furnace, pre-oxidizing the poly (acrylonitrile-styrene) copolymer for 3 hours at 220 ℃ in the air atmosphere, heating to 750 ℃ and carbonizing the poly (acrylonitrile-styrene) copolymer for 2 hours at high temperature to prepare the polymer-based nitrogen-phosphorus doped graphitized porous carbon 1.
Example 2
(1) Adding dichloromethane solvent with molecular formula of C into a reaction bottle 5 H 9 O 5 4-hydroxymethyl-1-oxo-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] P]Slowly dropwise adding acryloyl chloride into octane and triethylamine at the temperature of minus 5 ℃ according to the mass ratio of 175:112:100Stirring at constant speed for reacting for 10h, distilling under reduced pressure to remove solvent, washing with diethyl ether, adding methanol and distilled water, recrystallizing, and purifying to obtain molecular formula C 8 H 11 O 6 Acrylated 1-phospha-2, 6, 7-trioxabicyclo [2.2.2]An octane derivative.
(2) Adding N, N-dimethylformamide solvent, acrylonitrile, azobisisobutyronitrile and molecular formula C with the mass ratio of 100:1:0.14 into a reaction bottle 9 H 14 O 4 S 3 The RAFT reagent s, s ' -di (alpha, alpha ' -dimethyl-alpha ' -acetic acid) trithiocarbonate is placed in an atmosphere reaction device, the atmosphere reaction device comprises a heater, a water bath kettle is arranged above the heater, a base is arranged inside the water bath kettle, a clamping groove is fixedly connected above the base, a pulley is movably connected with a movable plate, a large reaction bottle and a small reaction bottle are arranged above the movable plate, a vent pipe is arranged above the water bath kettle, two ends of the vent pipe are movably connected with an air inlet valve and an air outlet valve respectively, the air inlet valve and the air outlet valve are heated to 85 ℃ under the nitrogen atmosphere to react for 10 hours, the solvent is removed by vacuum drying, and the polyacrylonitrile-based macromolecular chain transfer agent is prepared by washing and drying distilled water and methanol.
(3) Adding N, N-dimethylformamide solvent, styrene, acrylated 1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane derivative, polyacrylonitrile-based macromolecular chain transfer agent and initiator azodiisobutyronitrile into a reaction bottle, placing the mixture into an atmosphere reaction device, reacting for 18h at 85 ℃ under nitrogen atmosphere, vacuum drying to remove the solvent, washing with distilled water and methanol, and drying to obtain the phosphorus-containing monomer poly (acrylonitrile-styrene) copolymer.
(4) And (3) placing the poly (acrylonitrile-styrene) copolymer of the phosphorus-containing monomer in an atmosphere furnace, pre-oxidizing the poly (acrylonitrile-styrene) copolymer for 4 hours at 250 ℃ in an air atmosphere, heating to 750 ℃ and carbonizing the poly (acrylonitrile-styrene) copolymer for 3 hours at a high temperature to prepare the polymer-based nitrogen-phosphorus doped graphitized porous carbon 2.
Example 3
(1) Adding dichloromethane solvent with molecular formula of C into a reaction bottle 5 H 9 O 5 4-hydroxymethyl-1-oxy of P1-phospha-2, 6, 7-trioxabicyclo [2.2.2]Slowly dropwise adding acryloyl chloride into octane and triethylamine at the temperature of minus 5 ℃ at the mass ratio of 185:118:100, stirring at a constant speed for reaction for 8 hours, distilling under reduced pressure to remove the solvent, washing with diethyl ether, adding methanol and distilled water for recrystallization and purification, and obtaining the molecular formula C 8 H 11 O 6 Acrylated 1-phospha-2, 6, 7-trioxabicyclo [2.2.2]An octane derivative.
(2) Adding N, N-dimethylformamide solvent, acrylonitrile, azodiisobutyronitrile and the molecular formula C in a mass ratio of 100:1.25:0.16 into a reaction bottle 9 H 14 O 4 S 3 The RAFT reagent s, s ' -di (alpha, alpha ' -dimethyl-alpha ' -acetic acid) trithiocarbonate is placed in an atmosphere reaction device, the atmosphere reaction device comprises a heater, a water bath kettle is arranged above the heater, a base is arranged inside the water bath kettle, a clamping groove is fixedly connected above the base, a pulley is movably connected with a movable plate, a large reaction bottle and a small reaction bottle are arranged above the movable plate, a vent pipe is arranged above the water bath kettle, two ends of the vent pipe are movably connected with an air inlet valve and an air outlet valve respectively, the air inlet valve and the air outlet valve are heated to 80 ℃ under the nitrogen atmosphere to react for 15 hours, the solvent is removed by vacuum drying, and the polyacrylonitrile-based macromolecular chain transfer agent is prepared by washing and drying distilled water and methanol.
(3) Adding N, N-dimethylformamide solvent, styrene, acrylated 1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane derivative, polyacrylonitrile-based macromolecular chain transfer agent and initiator azodiisobutyronitrile into a reaction bottle, placing the mixture into an atmosphere reaction device, reacting for 18h at 85 ℃ under nitrogen atmosphere, vacuum drying to remove the solvent, washing with distilled water and methanol, and drying to obtain the phosphorus-containing monomer poly (acrylonitrile-styrene) copolymer.
(4) And (3) placing the poly (acrylonitrile-styrene) copolymer of the phosphorus-containing monomer in an atmosphere furnace, pre-oxidizing the poly (acrylonitrile-styrene) copolymer for 4 hours at 250 ℃ in an air atmosphere, heating the poly (acrylonitrile-styrene) copolymer to 780 ℃, and carbonizing the poly (acrylonitrile-styrene) copolymer for 2.5 hours at a high temperature to prepare the polymer-based nitrogen-phosphorus-doped graphitized porous carbon 3.
Example 4
(1) Adding dichloromethane solvent with molecular formula of C into a reaction bottle 5 H 9 O 5 4-hydroxymethyl-1-oxo-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] P]Slowly dropwise adding acryloyl chloride into octane and triethylamine at the temperature of minus 0 ℃ in the mass ratio of 190:120:100, uniformly stirring and reacting for 8 hours, distilling under reduced pressure to remove the solvent, washing with diethyl ether, adding methanol and distilled water for recrystallization and purification, and obtaining the molecular formula C 8 H 11 O 6 Acrylated 1-phospha-2, 6, 7-trioxabicyclo [2.2.2]An octane derivative.
(2) Adding N, N-dimethylformamide solvent, acrylonitrile, azodiisobutyronitrile and the molecular formula of C in a mass ratio of 100:1.5:0.12-0.18 into a reaction bottle 9 H 14 O 4 S 3 The RAFT reagent s, s ' -di (alpha, alpha ' -dimethyl-alpha ' -acetic acid) trithiocarbonate is placed in an atmosphere reaction device, the atmosphere reaction device comprises a heater, a water bath kettle is arranged above the heater, a base is arranged inside the water bath kettle, a clamping groove is fixedly connected above the base, a pulley is movably connected with a movable plate, a large reaction bottle and a small reaction bottle are arranged above the movable plate, a vent pipe is arranged above the water bath kettle, two ends of the vent pipe are movably connected with an air inlet valve and an air outlet valve respectively, the air inlet valve and the air outlet valve are heated to 85 ℃ under the nitrogen atmosphere to react for 20 hours, the solvent is removed by vacuum drying, and the polyacrylonitrile-based macromolecular chain transfer agent is prepared by washing and drying distilled water and methanol.
(3) Adding N, N-dimethylformamide solvent, styrene, acrylated 1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane derivative, polyacrylonitrile-based macromolecular chain transfer agent and initiator azodiisobutyronitrile into a reaction bottle, placing the mixture into an atmosphere reaction device, reacting for 24 hours at 90 ℃ under nitrogen atmosphere, vacuum drying to remove the solvent, washing with distilled water and methanol, and drying to obtain the phosphorus-containing monomer poly (acrylonitrile-styrene) copolymer.
(4) And (3) placing the poly (acrylonitrile-styrene) copolymer of the phosphorus-containing monomer in an atmosphere furnace, pre-oxidizing the poly (acrylonitrile-styrene) copolymer for 6 hours at 280 ℃ in an air atmosphere, and then heating the poly (acrylonitrile-styrene) copolymer to 800 ℃ for high-temperature carbonization treatment for 3 hours to prepare the polymer-based nitrogen-phosphorus doped graphitized porous carbon 4.
Comparative example 1
(1) Adding dichloromethane solvent with molecular formula of C into a reaction bottle 5 H 9 O 5 4-hydroxymethyl-1-oxo-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] P]Slowly dropwise adding acryloyl chloride into octane and triethylamine at the temperature of 0 ℃ in a mass ratio of 160:110:100, uniformly stirring and reacting for 10 hours, distilling under reduced pressure to remove a solvent, washing with diethyl ether, adding methanol and distilled water for recrystallization and purification, and obtaining a molecular formula C 8 H 11 O 6 Acrylated 1-phospha-2, 6, 7-trioxabicyclo [2.2.2]An octane derivative.
(2) Adding N, N-dimethylformamide solvent, acrylonitrile, azodiisobutyronitrile and the molecular formula C in a mass ratio of 100:0.5:0.1 into a reaction bottle 9 H 14 O 4 S 3 The RAFT reagent s, s ' -di (alpha, alpha ' -dimethyl-alpha ' -acetic acid) trithiocarbonate is placed in an atmosphere reaction device, the atmosphere reaction device comprises a heater, a water bath kettle is arranged above the heater, a base is arranged inside the water bath kettle, a clamping groove is fixedly connected above the base, a pulley is movably connected with a movable plate, a large reaction bottle and a small reaction bottle are arranged above the movable plate, a vent pipe is arranged above the water bath kettle, two ends of the vent pipe are movably connected with an air inlet valve and an air outlet valve respectively, the air inlet valve and the air outlet valve are heated to 80 ℃ under the nitrogen atmosphere to react for 15 hours, the solvent is removed by vacuum drying, and the polyacrylonitrile-based macromolecular chain transfer agent is prepared by washing and drying distilled water and methanol.
(3) Adding N, N-dimethylformamide solvent, styrene, acrylated 1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane derivative, polyacrylonitrile-based macromolecular chain transfer agent and initiator azodiisobutyronitrile into a reaction bottle, placing the mixture into an atmosphere reaction device, reacting for 18h at 85 ℃ under nitrogen atmosphere, vacuum drying to remove the solvent, washing with distilled water and methanol, and drying to obtain the phosphorus-containing monomer poly (acrylonitrile-styrene) copolymer.
(4) And (3) placing the poly (acrylonitrile-styrene) copolymer of the phosphorus-containing monomer in an atmosphere furnace, pre-oxidizing the poly (acrylonitrile-styrene) copolymer for 5 hours at 220 ℃ in an air atmosphere, heating to 750 ℃ and carbonizing the poly (acrylonitrile-styrene) copolymer for 3 hours at a high temperature to prepare the polymer-based nitrogen-phosphorus doped graphitized porous carbon comparative 1.
The polymer-based nitrogen-and phosphorus-doped graphitized porous carbon in the examples and the comparative examples are respectively mixed with acetylene black, polyvinylidene fluoride and N-methyl pyrrolidone solvent, and coated on the surface of copper foil, dried and punched to prepare the anode material of the lithium ion battery, wherein a lithium sheet is used as an anode material, a polypropylene porous membrane is used as a diaphragm, and 1mol/L of LiPF 6 The solution is used as electrolyte, a CR2032 button cell is assembled in an argon atmosphere, and constant current charge and discharge tests are carried out in a CT2001A cell test system, wherein the test standard is GB/T24533-2019.
Claims (4)
1. A polymer-based nitrogen-phosphorus doped graphitized porous carbon, characterized in that: the preparation method of the polymer-based nitrogen and phosphorus doped graphitized porous carbon comprises the following steps:
(1) Adding 4-hydroxymethyl-1-oxo-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane and triethylamine into a dichloromethane solvent, slowly dropwise adding acryloyl chloride at a temperature of between 10 ℃ below zero and 0 ℃ in a mass ratio of 170 to 190:110 to 120:100, and reacting for 5 to 10 hours to obtain an acrylated 1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane derivative;
(2) Adding acrylonitrile, azodiisobutyronitrile and RAFT reagent with the mass ratio of 100:0.75-1.5:0.12-0.18 into N, N-dimethylformamide solvent, placing the mixture into an atmosphere reaction device, heating to 75-85 ℃ in nitrogen atmosphere, and reacting for 10-20h to obtain the polyacrylonitrile-based macromolecular chain transfer agent;
(3) Adding styrene, acrylated 1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane derivative, polyacrylonitrile-based macromolecular chain transfer agent and initiator azodiisobutyronitrile into N, N-dimethylformamide solvent, and placing the mixture into an atmosphere reaction device to react for 12-24 hours at 80-90 ℃ in nitrogen atmosphere to prepare a phosphorus-containing monomer poly (acrylonitrile-styrene) copolymer;
(4) Placing the poly (acrylonitrile-styrene) copolymer containing phosphorus monomer in an atmosphere furnace, performing pre-oxidation and high-temperature carbonization treatment to prepare polymer-based nitrogen-phosphorus doped graphitized porous carbon, and applying the polymer-based nitrogen-phosphorus doped graphitized porous carbon to a lithium ion battery anode material;
the 4-hydroxymethyl-1-oxo-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] in step (1)]Octane of formula C 5 H 9 O 5 P, the structural formula isAcrylated 1-phospha-2, 6, 7-trioxabicyclo [2.2.2]Octane derivative of formula C 8 H 11 O 6 P is of the formula->
The RAFT reagent in the step (2) is s, s ' -di (alpha, alpha ' -dimethyl-alpha ' -acetic acid) trithiocarbonate, and the molecular formula is C 9 H 14 O 4 S 3 The structural formula is
The mass ratio of the styrene, the acrylated 1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane derivative, the polyacrylonitrile-based macromolecular chain transfer agent and the azodiisobutyronitrile in the step (3) is 100:20-40:8-15:0.1-0.2.
2. A polymer-based nitrogen-phosphorus doped graphitized porous carbon according to claim 1, wherein: the atmosphere reaction device in step (2) comprises a heater, a water bath is arranged above the heater, a base is arranged inside the water bath, a clamping groove is fixedly connected to the upper side of the base, a pulley is movably connected to the clamping groove, a large reaction bottle and a small reaction bottle are arranged above the moving plate, a vent pipe is arranged above the water bath, and two ends of the vent pipe are respectively movably connected with an air inlet valve and an air outlet valve.
3. A polymer-based nitrogen-phosphorus doped graphitized porous carbon according to claim 1, wherein: the pre-oxidation treatment in the step (4) is air atmosphere, and the pre-oxidation is carried out for 3-6 hours at 220-280 ℃.
4. A polymer-based nitrogen-phosphorus doped graphitized porous carbon according to claim 1, wherein: and (3) carbonizing the mixture at the high temperature in the step (4) in a nitrogen atmosphere at 750-800 ℃ for 2-3h.
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