CN112607733A - 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 43
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 35
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 25
- 239000011574 phosphorus Substances 0.000 title claims abstract description 25
- 229920000642 polymer Polymers 0.000 title claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims description 34
- 229910052757 nitrogen Inorganic materials 0.000 title claims description 17
- 238000002360 preparation method Methods 0.000 title claims description 7
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 238000003763 carbonization Methods 0.000 claims abstract description 8
- 229920001893 acrylonitrile styrene Polymers 0.000 claims abstract description 7
- 229920001577 copolymer Polymers 0.000 claims abstract description 7
- 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 7
- 238000006243 chemical reaction Methods 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 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 11
- 239000012298 atmosphere Substances 0.000 claims description 11
- 239000010406 cathode material Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 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
- YXVFYAGLYXEEHP-UHFFFAOYSA-N 2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane Chemical class O1CC2COP1OC2 YXVFYAGLYXEEHP-UHFFFAOYSA-N 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000012986 chain transfer agent Substances 0.000 claims description 8
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- -1 Acryloyl Chemical group 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 239000012989 trithiocarbonate Substances 0.000 claims description 2
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical compound [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 3
- 238000000034 method Methods 0.000 abstract description 12
- 239000011148 porous material Substances 0.000 abstract description 9
- 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 4
- 239000004793 Polystyrene Substances 0.000 abstract description 4
- 125000003342 alkenyl group Chemical group 0.000 abstract description 4
- 229920002223 polystyrene Polymers 0.000 abstract description 4
- 229920001169 thermoplastic Polymers 0.000 abstract description 3
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 3
- 239000004416 thermosoftening plastic Substances 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 2
- 238000005336 cracking Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 125000002743 phosphorus functional group Chemical group 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- AISZNMCRXZWVAT-UHFFFAOYSA-N 2-ethylsulfanylcarbothioylsulfanyl-2-methylpropanenitrile Chemical compound CCSC(=S)SC(C)(C)C#N AISZNMCRXZWVAT-UHFFFAOYSA-N 0.000 description 1
- 239000004966 Carbon aerogel Substances 0.000 description 1
- 239000012987 RAFT agent Substances 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 230000001276 controlling effect Effects 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
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 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
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
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- C01B32/205—Preparation
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- 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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- 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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- 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
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- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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Abstract
The invention relates to the technical field of lithium ion batteries, and discloses polymer-based nitrogen-phosphorus-doped graphitized porous carbon, wherein a poly (acrylonitrile-styrene) copolymer of a phosphorus-containing monomer is prepared by gasifying and cracking a polystyrene thermoplastic chain segment in a pre-oxidation process to generate a large amount of gas to escape from a matrix and leave a rich pore channel structure, a polyacrylonitrile thermosetting chain segment is crosslinked and cured in a high-temperature carbonization process to form a carbon skeleton, an alkenyl monomer of the phosphorus-containing group is thermally cracked to generate a phosphoric acid derivative in the pre-oxidation process, the phosphoric acid derivative has the function of catalyzing to form carbon, the high-temperature carbonization process is accelerated, the carbon forming rate is improved, and the carbon skeleton is promoted to form compact and continuous graphitized porous carbon, so that the nitrogen-phosphorus-doped graphitized porous carbon with rich pore structures and larger specific surface area is obtained, the electrochemical property, The pore structure and the specific surface area are adjusted.
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 large energy density and stable cycle performance, is a green and environment-friendly secondary battery, the cathode material of the lithium ion battery which is commercialized at present is mainly a graphite cathode material, but the theoretical specific capacity of graphite carbon is low and is only 370mAh/g, so that the development and application of the lithium ion battery are limited, and the cathode material which is researched in hot spots at present mainly comprises a metal oxide electrode material, a metal alloy cathode material, a silicon-based cathode material and a carbon cathode material, wherein the carbon cathode material such as carbon aerogel, porous carbon, graphene, carbon nano tubes and the like has excellent electrochemical performance, 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 channel structures and an ultrahigh specific surface area, and has rich sites for lithium removal and lithium insertion, good electronic conductivity and lithium ion diffusion coefficient, so that the novel porous carbon with excellent performance is synthesized and developed at present to meet the requirement of being applied to a lithium ion battery cathode material and become a research hotspot, wherein the heteroatom doping has the effects of regulating the pore structure and the specific surface area of the porous carbon, regulating the electronic arrangement, improving the electrochemical property and the like through one of the most effective methods of the nitrogen, sulfur, phosphorus and other heteroatom doping.
Technical problem to be solved
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 has higher specific capacity and excellent rate capability.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of polymer-based nitrogen and phosphorus doped graphitized porous carbon comprises the following steps:
(1) adding a 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 ℃ in a mass ratio of 170-110-100, uniformly stirring for reaction for 5 to 10 hours, carrying out reduced pressure distillation to remove the solvent, washing with diethyl ether, adding methanol and distilled water for recrystallization and purification, and preparing the acryloyl esterified 1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane derivative.
(2) Adding an N, N-dimethylformamide solvent, acrylonitrile, azodiisobutyronitrile and a RAFT reagent in a 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 prepare the polyacrylonitrile-based macromolecular chain transfer agent.
(3) Adding an N, N-dimethylformamide solvent, adding styrene, an acryloyl esterified 1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane derivative, a polyacrylonitrile-based macromolecular chain transfer agent and an initiator azobisisobutyronitrile into a reaction bottle, placing the reaction bottle in an atmosphere reaction device, reacting for 12-24h at 80-90 ℃ in the nitrogen atmosphere, vacuum drying to remove the solvent, washing with distilled water and methanol, and drying to prepare the phosphorus monomer-containing poly (acrylonitrile-styrene) copolymer.
(4) The poly (acrylonitrile-styrene) copolymer containing phosphorus monomers is placed in an atmosphere furnace for pre-oxidation and high-temperature carbonization treatment to prepare polymer-based nitrogen and phosphorus doped graphitized porous carbon which is applied to a lithium ion battery cathode material.
Preferably, the 4-hydroxymethyl-1-oxo-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] in the step (1)]Octane having the formula C5H9O5P has a structural formula of
Acryloyl esterified 1-phospha-2, 6, 7-trioxabicyclo [2.2.2]Octane derivatives of formula C8H11O6P is of the structural formula
Preferably, the RAFT agent in the step (2) is s, s ' -di (alpha, alpha ' -dimethyl-alpha ' -acetic acid) trithiocarbonate with the molecular formula of C9H14O4S3Structural formula is
Preferably, the atmosphere reaction device in step (2) includes a heater, a water bath is arranged above the heater, a base is arranged inside the water bath, a clamping groove is fixedly connected above 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 acryloyl esterified 1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane derivative, the polyacrylonitrile-based macromolecular chain transfer agent and the azobisisobutyronitrile 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 carried out for 3 to 6 hours at the temperature of 220 ℃ and 280 ℃.
Preferably, the high-temperature carbonization treatment in the step (4) is performed in a nitrogen atmosphere at 750-800 ℃ for 2-3 h.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
according to the polymer-based nitrogen and phosphorus doped graphitized porous carbon, acryloyl esterified 1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane derivatives are used as alkenyl monomers containing phosphorus groups, a polyacrylonitrile-based macromolecular chain transfer agent is used as a nitrogen-containing monomer, and the nitrogen-containing monomer and polystyrene are copolymerized by a high-efficiency controllable RAFT reversible addition-fragmentation chain transfer polymerization method to obtain a poly (acrylonitrile-styrene) copolymer containing the phosphorus monomer, so that nitrogen and phosphorus are controllably and highly distributed in polymer molecular chains.
The polymer-based nitrogen and phosphorus-doped graphitized porous carbon comprises a polystyrene thermoplastic chain segment and a polyacrylonitrile thermosetting chain segment in a poly (acrylonitrile-styrene) copolymer molecular chain of a phosphorus-containing monomer, wherein the polystyrene thermoplastic chain segment is gasified and cracked in the pre-oxidation process to generate a large amount of gas which escapes from a matrix and leave a rich pore channel structure, the polyacrylonitrile thermosetting chain segment is crosslinked and cured in the high-temperature carbonization process to form a carbon skeleton, in the pre-oxidation process, the alkenyl monomer of the phosphorus-containing group is thermally cracked to generate a phosphoric acid derivative, the phosphoric acid derivative has the function of catalyzing to form carbon, the high-temperature carbonization process is accelerated, the carbon forming rate is improved, the carbon skeleton is promoted to form compact and continuous graphitized porous carbon, and thus 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 have good electrochemical properties, pore structures and specific The method has the advantages that the promotion effect is achieved, the doping amount of nitrogen and phosphorus and the controllable adjustment of a pore structure are achieved through the controllable reversible addition-fragmentation chain transfer polymerization method by controlling the amount of the alkenyl monomer containing the phosphorus group and the amount of the polyacrylonitrile-based macromolecular chain transfer agent, and the polymer-based nitrogen and phosphorus doped graphitized porous carbon has higher actual specific capacity and excellent rate capability.
Drawings
FIG. 1 is a schematic view of the structure of an atmosphere reaction apparatus;
FIG. 2 is an enlarged schematic view of the base;
fig. 3 is a schematic diagram of moving plate adjustment.
1-a heater; 2-water bath; 3-a base; 4-a card slot; 5-a pulley; 6, moving a board; 7-large reaction bottle; 8-small reaction bottle; 9-a breather pipe; 10-an air inlet valve; 11-gas outlet valve.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a preparation method of 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 bottle5H9O54-hydroxymethyl-1-oxo-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] of P]Octane and triethylamine are slowly dripped with acryloyl chloride at the temperature of between 10 below zero and 0 ℃ below zero in a mass ratio of 170-110-120: 100, the three are stirred at a constant speed for reaction for 5 to 10 hours, the solvent is removed by reduced pressure distillation, ether is used for washing, methanol and distilled water are added for recrystallization and purification, and the molecular formula C is prepared8H11O6Acryloylation of P1-phospha-2, 67-trioxabicyclo [2.2.2]An octane derivative.
(2) Adding N, N-dimethylformamide solvent, acrylonitrile, azodiisobutyronitrile and C with the molecular formula of 100:0.75-1.5:0.12-0.18 by mass ratio into a reaction bottle9H14O4S3The 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 is arranged above the heater, a base is arranged inside the water bath, a clamping groove is fixedly connected above the base, the clamping groove is movably connected with a pulley, the pulley is movably connected with a moving plate, a large reaction bottle and a small reaction bottle are arranged above the moving plate, a vent pipe is arranged above the water bath, two ends of the vent pipe are respectively and movably connected with an air inlet valve and an air outlet valve, the reaction is carried out for 10-20h by heating to 75-85 ℃ in a nitrogen atmosphere, solvents are removed by vacuum drying, and the polyacrylonitrile-based macromolecular chain transfer agent is prepared by washing and drying by using distilled.
(3) Adding an N, N-dimethylformamide solvent, adding styrene, an acryloyl esterified 1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane derivative, a polyacrylonitrile-based macromolecular chain transfer agent and an initiator azobisisobutyronitrile according to the mass ratio of 100:20-40:8-15:0.1-0.2 into a reaction bottle, placing the mixture into an atmosphere reaction device, reacting for 12-24h at 80-90 ℃ in a nitrogen atmosphere, drying in vacuum to remove the solvent, washing with distilled water and methanol, and drying to obtain the phosphorus monomer-containing poly (acrylonitrile-styrene) copolymer.
(4) The preparation method comprises the steps of placing a poly (acrylonitrile-styrene) copolymer containing a phosphorus monomer in an atmosphere furnace, carrying out pre-oxidation treatment for 3-6h at 280 ℃ in the air atmosphere, then heating to 800 ℃ at 750 ℃ and carrying out high-temperature carbonization treatment for 2-3h to prepare polymer-based nitrogen and phosphorus doped graphitized porous carbon, and applying the polymer-based nitrogen and phosphorus doped graphitized porous carbon to a lithium ion battery cathode material.
Example 1
(1) Adding dichloromethane solvent with molecular formula of C into a reaction bottle5H9O54-hydroxymethyl-1-oxo-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] of P]Octane and triethylamine are added, acryloyl chloride is slowly dropped at the temperature of 0 ℃, and the mass ratio of the octane to the triethylamine is 170:110:100Stirring at constant speed for 5h, distilling under reduced pressure to remove solvent, washing with diethyl ether, adding methanol and distilled water, recrystallizing and purifying to obtain molecular formula C8H11O6Acryloylation of P to 1-phospha-2, 6, 7-trioxabicyclo [2.2.2]An octane derivative.
(2) Adding N, N-dimethylformamide solvent, acrylonitrile, azodiisobutyronitrile and C with the molecular formula of 100:0.75:0.12 by mass into a reaction bottle9H14O4S3The 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 is arranged above the heater, a base is arranged inside the water bath, a clamping groove is fixedly connected above the base, the clamping groove is movably connected with a pulley, the pulley is movably connected with a moving plate, a large reaction bottle and a small reaction bottle are arranged above the moving plate, a vent pipe is arranged above the water bath, two ends of the vent pipe are respectively and movably connected with an air inlet valve and an air outlet valve, the reaction is carried out for 10 hours by heating to 75 ℃ in a nitrogen atmosphere, solvents are removed by vacuum drying, and the polyacrylonitrile-based macromolecular chain transfer agent is prepared by washing and drying by using distilled.
(3) Adding an N, N-dimethylformamide solvent, adding styrene, an acryloyl esterified 1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane derivative, a polyacrylonitrile-based macromolecular chain transfer agent and an initiator azobisisobutyronitrile according to the mass ratio of 100:20:8:0.1 into a reaction bottle, placing the reaction bottle in an atmosphere reaction device, reacting for 12 hours at 80 ℃ in a nitrogen atmosphere, vacuum drying to remove the solvent, washing with distilled water and methanol, and drying to prepare the poly (acrylonitrile-styrene) copolymer containing the phosphorus monomer.
(4) Placing a poly (acrylonitrile-styrene) copolymer containing a phosphorus monomer in an atmosphere furnace, firstly carrying out preoxidation treatment for 3h at 220 ℃ in the air atmosphere, then heating to 750 ℃, and carrying out high-temperature carbonization treatment for 2h to prepare the polymer-based nitrogen and phosphorus doped graphitized porous carbon 1.
Example 2
(1) Adding dichloromethane solvent with molecular formula of C into a reaction bottle5H9O54-hydroxymethyl-1-oxyl of PSubstituted-1-phospha-2, 6, 7-trioxabicyclo [2.2.2]Octane and triethylamine are added, acryloyl chloride is slowly dropped at the temperature of minus 5 ℃, the mass ratio of the three is 175:112:100, the mixture is stirred at a constant speed for reaction for 10 hours, the solvent is removed by reduced pressure distillation, the mixture is washed by ether, methanol and distilled water are added for recrystallization and purification, and the molecular formula C is prepared8H11O6Acryloylation of P to 1-phospha-2, 6, 7-trioxabicyclo [2.2.2]An octane derivative.
(2) Adding N, N-dimethylformamide solvent, acrylonitrile, azodiisobutyronitrile and C with the molecular formula of 100:1:0.14 by mass into a reaction bottle9H14O4S3The 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 is arranged above the heater, a base is arranged inside the water bath, a clamping groove is fixedly connected above the base, the clamping groove is movably connected with a pulley, the pulley is movably connected with a moving plate, a large reaction bottle and a small reaction bottle are arranged above the moving plate, a vent pipe is arranged above the water bath, two ends of the vent pipe are respectively and movably connected with an air inlet valve and an air outlet valve, the reaction is carried out for 10 hours by heating to 85 ℃ in a nitrogen atmosphere, solvents are removed by vacuum drying, and the polyacrylonitrile-based macromolecular chain transfer agent is prepared by washing and drying by using distilled.
(3) Adding an N, N-dimethylformamide solvent, adding styrene, an acryloyl esterified 1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane derivative, a polyacrylonitrile-based macromolecular chain transfer agent and an initiator azobisisobutyronitrile in a mass ratio of 100:25:10:0.15 into a reaction bottle, placing the reaction bottle in an atmosphere reaction device, reacting for 18 hours at 85 ℃ in a nitrogen atmosphere, vacuum drying to remove the solvent, washing with distilled water and methanol, and drying to prepare the poly (acrylonitrile-styrene) copolymer containing the phosphorus monomer.
(4) The preparation method comprises the steps of putting a poly (acrylonitrile-styrene) copolymer containing a phosphorus monomer into an atmosphere furnace, carrying out pre-oxidation treatment for 4 hours at 250 ℃ in the air atmosphere, then heating to 750 ℃, and carrying out high-temperature carbonization treatment for 3 hours to prepare the polymer-based nitrogen and phosphorus doped graphitized porous carbon 2.
Example 3
(1) Adding dichloromethane solvent with molecular formula of C into a reaction bottle5H9O54-hydroxymethyl-1-oxo-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] of P]Octane and triethylamine, slowly dripping acryloyl chloride at-5 ℃ in a mass ratio of 185:118:100, uniformly stirring for 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 to obtain the molecular formula C8H11O6Acryloylation of P to 1-phospha-2, 6, 7-trioxabicyclo [2.2.2]An octane derivative.
(2) Adding N, N-dimethylformamide solvent, acrylonitrile, azodiisobutyronitrile and C with the molecular formula of 100:1.25:0.16 by mass into a reaction bottle9H14O4S3The 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 is arranged above the heater, a base is arranged inside the water bath, a clamping groove is fixedly connected above the base, the clamping groove is movably connected with a pulley, the pulley is movably connected with a moving plate, a large reaction bottle and a small reaction bottle are arranged above the moving plate, a vent pipe is arranged above the water bath, two ends of the vent pipe are respectively and movably connected with an air inlet valve and an air outlet valve, the heating is carried out to 80 ℃ in a nitrogen atmosphere, the reaction is carried out for 15 hours, the solvent is removed by vacuum drying, the product is washed and dried by using distilled water and methanol.
(3) Adding an N, N-dimethylformamide solvent, adding styrene, an acryloyl esterified 1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane derivative, a polyacrylonitrile-based macromolecular chain transfer agent and an initiator azobisisobutyronitrile in a mass ratio of 100:32:12:0.17 into a reaction bottle, placing the reaction bottle in an atmosphere reaction device, reacting for 18 hours at 85 ℃ in a nitrogen atmosphere, vacuum drying to remove the solvent, washing with distilled water and methanol, and drying to prepare the poly (acrylonitrile-styrene) copolymer containing the phosphorus monomer.
(4) Placing a poly (acrylonitrile-styrene) copolymer containing a phosphorus monomer in an atmosphere furnace, firstly carrying out pre-oxidation treatment for 4h at 250 ℃ in the air atmosphere, then heating to 780 ℃, and carrying out high-temperature carbonization treatment for 2.5h to prepare the polymer-based nitrogen and phosphorus doped graphitized porous carbon 3.
Example 4
(1) Adding dichloromethane solvent with molecular formula of C into a reaction bottle5H9O54-hydroxymethyl-1-oxo-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] of P]Octane and triethylamine are slowly added with acryloyl chloride dropwise at the temperature of minus 0 ℃ in a mass ratio of 190:120:100, the three are stirred at a constant speed for reaction for 8 hours, the solvent is removed by reduced pressure distillation, the ethyl ether is used for washing, methanol and distilled water are added for recrystallization and purification, and the molecular formula C is prepared8H11O6Acryloylation of P to 1-phospha-2, 6, 7-trioxabicyclo [2.2.2]An octane derivative.
(2) Adding N, N-dimethylformamide solvent, acrylonitrile, azodiisobutyronitrile and C with the molecular formula of 100:1.5:0.12-0.18 by mass ratio into a reaction bottle9H14O4S3The 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 is arranged above the heater, a base is arranged inside the water bath, a clamping groove is fixedly connected above the base, the clamping groove is movably connected with a pulley, the pulley is movably connected with a moving plate, a large reaction bottle and a small reaction bottle are arranged above the moving plate, a vent pipe is arranged above the water bath, two ends of the vent pipe are respectively and movably connected with an air inlet valve and an air outlet valve, the mixture is heated to 85 ℃ in a nitrogen atmosphere and reacts for 20 hours, a solvent is removed by vacuum drying, and the mixture is washed and dried by using distilled water and methanol to prepare the polyacrylonitrile-.
(3) Adding an N, N-dimethylformamide solvent, adding styrene, an acryloyl esterified 1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane derivative, a polyacrylonitrile-based macromolecular chain transfer agent and an initiator azobisisobutyronitrile in a mass ratio of 100:40:15:0.2 into a reaction bottle, placing the reaction bottle in an atmosphere reaction device, reacting for 24 hours at 90 ℃ in a nitrogen atmosphere, vacuum drying to remove the solvent, washing with distilled water and methanol, and drying to prepare the poly (acrylonitrile-styrene) copolymer containing the phosphorus monomer.
(4) Placing a poly (acrylonitrile-styrene) copolymer containing a phosphorus monomer in an atmosphere furnace, firstly carrying out preoxidation treatment for 6h at 280 ℃ in the air atmosphere, then heating to 800 ℃, and carrying out high-temperature carbonization treatment for 3h to prepare the polymer-based nitrogen and phosphorus doped graphitized porous carbon 4.
Comparative example 1
(1) Adding dichloromethane solvent with molecular formula of C into a reaction bottle5H9O54-hydroxymethyl-1-oxo-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] of P]Octane and triethylamine are slowly added with acryloyl chloride dropwise at the temperature of 0 ℃ in a mass ratio of 160:110:100, the three are stirred at a constant speed for reaction for 10 hours, the solvent is removed by reduced pressure distillation, ether is used for washing, methanol and distilled water are added for recrystallization and purification, and the molecular formula C is prepared8H11O6Acryloylation of P to 1-phospha-2, 6, 7-trioxabicyclo [2.2.2]An octane derivative.
(2) Adding N, N-dimethylformamide solvent, acrylonitrile, azodiisobutyronitrile and C with the molecular formula of 100:0.5:0.1 by mass into a reaction bottle9H14O4S3The 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 is arranged above the heater, a base is arranged inside the water bath, a clamping groove is fixedly connected above the base, the clamping groove is movably connected with a pulley, the pulley is movably connected with a moving plate, a large reaction bottle and a small reaction bottle are arranged above the moving plate, a vent pipe is arranged above the water bath, two ends of the vent pipe are respectively and movably connected with an air inlet valve and an air outlet valve, the heating is carried out to 80 ℃ in a nitrogen atmosphere, the reaction is carried out for 15 hours, the solvent is removed by vacuum drying, the product is washed and dried by using distilled water and methanol.
(3) Adding an N, N-dimethylformamide solvent, adding styrene, an acryloyl esterified 1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane derivative, a polyacrylonitrile-based macromolecular chain transfer agent and an initiator azobisisobutyronitrile in a mass ratio of 100:15:6:0.08 into a reaction bottle, placing the reaction bottle in an atmosphere reaction device, reacting for 18 hours at 85 ℃ in a nitrogen atmosphere, vacuum drying to remove the solvent, washing with distilled water and methanol, and drying to prepare the poly (acrylonitrile-styrene) copolymer containing the phosphorus monomer.
(4) Placing a poly (acrylonitrile-styrene) copolymer containing a phosphorus monomer in an atmosphere furnace, firstly carrying out preoxidation treatment for 5h at 220 ℃ in the air atmosphere, then heating to 750 ℃, and carrying out high-temperature carbonization treatment for 3h to prepare polymer-based nitrogen and phosphorus doped graphitized porous carbon contrast 1.
Respectively mixing polymer-based nitrogen and phosphorus doped graphitized porous carbon in the examples and the comparative examples with acetylene black, polyvinylidene fluoride and N-methyl pyrrolidone solvents, coating the mixture on the surface of copper foil, drying and stamping to prepare a negative electrode material of a lithium ion battery, taking a lithium sheet as a positive electrode material and a polypropylene porous membrane as a diaphragm, and 1mol/L LiPF6The solution is used as electrolyte, a CR2032 button cell is assembled in argon atmosphere, and a constant current charge-discharge test is carried out in a CT2001A cell test system, wherein the test standard is GB/T243358-2019.
Claims (7)
1. A polymer-based nitrogen and phosphorus doped graphitized porous carbon is 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 the temperature of between-10 and-0 ℃, reacting for 5 to 10 hours, wherein the mass ratio of the three is 170-;
(2) adding acrylonitrile, azobisisobutyronitrile and RAFT reagent in a mass ratio of 100:0.75-1.5:0.12-0.18 into an N, N-dimethylformamide solvent, placing the mixture in an atmosphere reaction device, heating the mixture to 75-85 ℃ in a nitrogen atmosphere, and reacting for 10-20 hours to prepare the polyacrylonitrile-based macromolecular chain transfer agent;
(3) adding styrene, acryloyl esterified 1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane derivative, polyacrylonitrile-based macromolecular chain transfer agent and initiator azobisisobutyronitrile into an N, N-dimethylformamide solvent, placing the mixture into an atmosphere reaction device, and reacting at 80-90 ℃ for 12-24 hours in a nitrogen atmosphere to prepare a phosphorus monomer-containing poly (acrylonitrile-styrene) copolymer;
(4) the poly (acrylonitrile-styrene) copolymer containing phosphorus monomers is placed in an atmosphere furnace for pre-oxidation and high-temperature carbonization treatment to prepare polymer-based nitrogen and phosphorus doped graphitized porous carbon which is applied to a lithium ion battery cathode material.
2. The polymer-based nitrogen-phosphorus-doped graphitized porous carbon according to claim 1, wherein: the 4-hydroxymethyl-1-oxo-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] in the step (1)]Octane having the formula C5H9O5P has a structural formula of
Acryloyl esterified 1-phospha-2, 6, 7-trioxabicyclo [2.2.2]Octane derivatives of formula C8H11O6P is of the structural formula
3. The polymer-based nitrogen-phosphorus-doped graphitized porous carbon according to claim 1, wherein: the RAFT reagent in the step (2) is s, s ' -di (alpha, alpha ' -dimethyl-alpha ' -acetic acid) trithiocarbonate with a molecular formula of C9H14O4S3Structural formula is
4. The polymer-based nitrogen-phosphorus-doped graphitized porous carbon according to claim 1, wherein: 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 above 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.
5. The polymer-based nitrogen-phosphorus-doped graphitized porous carbon according to claim 1, wherein: the mass ratio of the styrene, the acryloyl esterified 1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane derivative, the polyacrylonitrile-based macromolecular chain transfer agent and the azobisisobutyronitrile in the step (3) is 100:20-40:8-15: 0.1-0.2.
6. The polymer-based nitrogen-phosphorus-doped graphitized porous carbon according to claim 1, wherein: the pre-oxidation treatment in the step (4) is an air atmosphere and is performed for 3-6h at the temperature of 220-280 ℃.
7. The polymer-based nitrogen-phosphorus-doped graphitized porous carbon according to claim 1, wherein: the high-temperature carbonization treatment in the step (4) is carried out for 2-3h at the temperature of 750-800 ℃ in a nitrogen atmosphere.
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|---|---|---|---|---|
| CN115010118A (en) * | 2022-06-06 | 2022-09-06 | 武汉理工大学 | Nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene, and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1962703A (en) * | 2006-11-30 | 2007-05-16 | 中国科学院长春应用化学研究所 | Preparation method of acrylic nitrile homopolymer (copolymer) |
| CN102746439A (en) * | 2012-07-12 | 2012-10-24 | 华东理工大学 | Preparation method of end group functionalized acrylonitrile homopolymer or copolymer |
| US20120328880A1 (en) * | 2009-12-24 | 2012-12-27 | Toray Industries, Inc. | Carbon microparticle and process for producing thereof |
| CN104371116A (en) * | 2014-11-04 | 2015-02-25 | 南京林业大学 | Preparation method and application of lignin-based intumescent flame retardant |
| WO2015133461A1 (en) * | 2014-03-03 | 2015-09-11 | 日産化学工業株式会社 | Ion complex material having function for preventing adherence to biological material |
| CN111621112A (en) * | 2020-06-04 | 2020-09-04 | 广州科苑新型材料有限公司 | Antibacterial halogen-free flame-retardant static dissipative HIPS material and preparation method thereof |
| CN111847441A (en) * | 2020-07-09 | 2020-10-30 | 南京理工大学 | Method for preparing phosphorus and nitrogen co-doped graphitized porous carbon by one-pot method |
-
2020
- 2020-12-16 CN CN202011487642.0A patent/CN112607733B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1962703A (en) * | 2006-11-30 | 2007-05-16 | 中国科学院长春应用化学研究所 | Preparation method of acrylic nitrile homopolymer (copolymer) |
| US20120328880A1 (en) * | 2009-12-24 | 2012-12-27 | Toray Industries, Inc. | Carbon microparticle and process for producing thereof |
| CN102746439A (en) * | 2012-07-12 | 2012-10-24 | 华东理工大学 | Preparation method of end group functionalized acrylonitrile homopolymer or copolymer |
| WO2015133461A1 (en) * | 2014-03-03 | 2015-09-11 | 日産化学工業株式会社 | Ion complex material having function for preventing adherence to biological material |
| CN104371116A (en) * | 2014-11-04 | 2015-02-25 | 南京林业大学 | Preparation method and application of lignin-based intumescent flame retardant |
| CN111621112A (en) * | 2020-06-04 | 2020-09-04 | 广州科苑新型材料有限公司 | Antibacterial halogen-free flame-retardant static dissipative HIPS material and preparation method thereof |
| CN111847441A (en) * | 2020-07-09 | 2020-10-30 | 南京理工大学 | Method for preparing phosphorus and nitrogen co-doped graphitized porous carbon by one-pot method |
Non-Patent Citations (5)
| Title |
|---|
| JI-HAN LEE ET.AL: "Preparation and electrochemical behaviors ofstyrene–acrylonitrile-based porous carbon electrodes", vol. 113, pages 23 - 28 * |
| 朱道吉;李小宝;周正发;任凤梅;徐卫兵: "膨胀型阻燃剂APP/MPR/PEPA的制备及其在ABS中的应用" * |
| 朱道吉;李小宝;周正发;任凤梅;徐卫兵: "膨胀型阻燃剂APP/MPR/PEPA的制备及其在ABS中的应用", 塑料工业, vol. 42, no. 003, pages 107 - 110 * |
| 王豪: "氮磷共掺杂碳材料制备及电催化氮气还原反应研究", no. 6, pages 015 - 39 * |
| 闫莉: "含磷、含硅丙烯酸酯共聚苯乙烯的燃烧和热分解性能研究", vol. 42, no. 11, pages 175 - 177 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115010118A (en) * | 2022-06-06 | 2022-09-06 | 武汉理工大学 | Nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene, and preparation method and application thereof |
| CN115010118B (en) * | 2022-06-06 | 2024-01-23 | 武汉理工大学 | Nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene and preparation method and application thereof |
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