CN112591730A - Nitrogen-doped porous carbon cathode material with adjustable pore diameter and porosity and preparation method thereof - Google Patents
Nitrogen-doped porous carbon cathode material with adjustable pore diameter and porosity and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 47
- 239000011148 porous material Substances 0.000 title claims abstract description 27
- 239000010406 cathode material Substances 0.000 title claims description 17
- 238000002360 preparation method Methods 0.000 title claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 67
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 63
- 229920001661 Chitosan Polymers 0.000 claims abstract description 41
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000010405 anode material Substances 0.000 claims abstract description 11
- 238000003763 carbonization Methods 0.000 claims abstract description 10
- 238000007725 thermal activation Methods 0.000 claims abstract description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 48
- 239000012298 atmosphere Substances 0.000 claims description 47
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000001354 calcination Methods 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 14
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 125000000304 alkynyl group Chemical group 0.000 claims description 6
- XXFUZSHTIOFGNV-UHFFFAOYSA-N 1-bromoprop-1-yne Chemical compound CC#CBr XXFUZSHTIOFGNV-UHFFFAOYSA-N 0.000 claims description 4
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 claims description 4
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 4
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 4
- 229960005055 sodium ascorbate Drugs 0.000 claims description 4
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 4
- 238000004227 thermal cracking Methods 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 2
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims 2
- 238000005096 rolling process Methods 0.000 claims 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000003125 aqueous solvent Substances 0.000 claims 1
- 238000001132 ultrasonic dispersion Methods 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 abstract description 13
- 239000011593 sulfur Substances 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 10
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 8
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 229920001021 polysulfide Polymers 0.000 abstract description 3
- 239000005077 polysulfide Substances 0.000 abstract description 3
- 150000008117 polysulfides Polymers 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 230000001351 cycling effect Effects 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 238000003756 stirring Methods 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 238000001994 activation Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000003480 eluent Substances 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 125000001399 1,2,3-triazolyl group Chemical group N1N=NC(=C1)* 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Chemical group C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 1
- 238000006736 Huisgen cycloaddition reaction Methods 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012650 click reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/10—Finely divided sulfur, e.g. sublimed sulfur, flowers of sulfur
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
Abstract
The invention relates to the technical field of lithium sulfur batteries, and discloses a nitrogen-doped porous carbon anode material with adjustable pore diameter and porosity, polyethylene glycol is connected through covalent bonds and highly dispersed in a cross-linked chitosan matrix, the polyethylene glycol with poor thermal stability is thermally cracked and gasified to escape in the process of thermal activation under certain pressure, a large amount of highly dispersed mesoporous and porous structures are formed in the cross-linked chitosan matrix, the nitrogen-doped porous carbon with adjustable pore diameter and porosity is obtained through high-temperature carbonization by regulating the molecular weight of the polyethylene glycol, the nitrogen-doped porous carbon has rich pore structures and a large amount of active adsorption sites, polysulfide has good chemical adsorption effect, the loss of active sulfur substances is avoided and the active sulfur substances are dissolved in electrolyte, the shuttle effect is reduced, and the nitrogen-doped porous carbon provides a buffer layer for the volume expansion of a sulfur anode, so that the cycle stability of the anode material is improved, exhibits an ultra-high practical specific capacity and excellent electrochemical cycling stability.
Description
Technical Field
The invention relates to the technical field of lithium-sulfur batteries, in particular to a nitrogen-doped porous carbon anode material with adjustable pore diameter and porosity and a preparation method thereof.
Background
The lithium-sulfur battery is one of lithium batteries, generally, sulfur element is used as a battery anode, metal lithium is used as a cathode, the lithium-sulfur battery has ultrahigh theoretical specific capacity and theoretical specific energy, and the capacity is much larger than that of a lithium cobaltate battery widely applied commercially, and a sulfur simple substance has the characteristics of abundant reserves, low price, environmental friendliness and the like, so that the lithium-sulfur battery is a high-specific-energy lithium battery with huge development potential.
However, the lithium sulfur battery is commercially difficult to be applied on a large scale at present, mainly because the elemental sulfur is a non-conductive substance, the conductivity is very poor, and the high rate performance of the lithium sulfur battery is not facilitated, and in the charging and discharging process of the sulfur positive electrode material, the volume expansion phenomenon is serious, so that the electrochemical cycle stability of the battery is greatly influenced, and in the charging and discharging process, polysulfide generated by the elemental sulfur reaction is easily dissolved into the electrolyte to form a shuttle effect, so that the loss of active sulfur substances is caused, and the actual specific capacity of the battery is seriously reduced.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a nitrogen-doped porous carbon anode material with adjustable pore diameter and porosity and a preparation method thereof, and solves the problems of poor conductivity, shuttle effect and the like of a sulfur anode material.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: the preparation method of the nitrogen-doped porous carbon cathode material with adjustable pore diameter and porosity comprises the following steps:
(1) adding a toluene solvent, polyethylene glycol and triethylamine into a reaction bottle, stirring and dissolving, slowly adding a toluene solution of p-toluenesulfonyl chloride, stirring and reacting at a constant speed for 12-24h at room temperature, distilling under reduced pressure to remove the solvent, and separating and purifying by column chromatography, wherein an eluent is dichloromethane and methanol is 5-10:1, so as to prepare the monosulfonyl polyethylene glycol.
(2) Adding N, N-dimethylformamide solvent, monosulfonyl polyethylene glycol and sodium azide in a mass ratio of 100:2-12 into a reaction bottle, heating to 80-110 ℃, stirring at a constant speed, refluxing for reaction for 30-40h, adding distilled water and dichloromethane for extraction, removing an organic phase, and drying to obtain the monosulfonyl polyethylene glycol.
(3) Adding a sodium hydroxide aqueous solution and an isopropanol solvent into a reaction bottle, adding carboxymethyl chitosan, performing ultrasonic dispersion uniformly, adding bromopropyne, heating to 65-75 ℃, uniformly stirring for reaction for 4-8h, dropwise adding dilute hydrochloric acid to adjust the pH value to be neutral, adding an acetone solvent until a large amount of precipitate is separated out, filtering the solvent, washing with ethanol, and drying to obtain the chitosan with side chains containing alkynyl.
(4) Adding a distilled water solvent and chitosan with alkynyl side chains into a reaction bottle, adding copper sulfate, sodium ascorbate and mono-azido polyethylene glycol after uniformly dispersing by ultrasound, stirring at a constant speed for reaction for 20-40h, removing the solvent by reduced pressure distillation, and dialyzing and purifying a solid product to prepare the polyethylene glycol grafted chitosan.
(5) Adding distilled water solvent, polyethylene glycol grafted chitosan and glutaraldehyde into a reaction bottle, heating to 40-60 ℃, uniformly stirring for reaction for 12-24h, carrying out reduced pressure distillation to remove the solvent, washing with ethanol and drying to prepare the polyethylene glycol grafted crosslinked chitosan.
(6) And (3) placing the polyethylene glycol grafted crosslinked chitosan in an atmosphere resistance furnace to carry out a thermal activation process and a high-temperature carbonization process, so as to prepare the nitrogen-doped porous carbon with adjustable aperture and porosity.
(7) Uniformly mixing the nitrogen-doped porous carbon with adjustable aperture and porosity with sublimed sulfur, placing the mixture in a reaction kettle, heating the mixture to 160 ℃, carrying out heat treatment for 10-15h, placing the mixed product in an atmosphere resistance furnace, and carrying out heat treatment for 1-2h at 200 ℃ in the nitrogen atmosphere to prepare the nitrogen-doped porous carbon anode material with adjustable aperture and porosity.
Preferably, the molecular weight of the polyethylene glycol in the step (1) is 1000-6000, and the mass ratio of the polyethylene glycol to the triethylamine to the p-toluenesulfonyl chloride is 100:3-20:1.5-10
Preferably, the mass ratio of the carboxymethyl chitosan to the bromopropyne in the step (3) is 10: 20-30.
Preferably, the mass ratio of the side chain containing alkynyl chitosan, copper sulfate, sodium ascorbate and mono-azido polyethylene glycol in the step (4) is 100:0.8-1.2:12-15: 100-.
Preferably, the mass ratio of the polyethylene glycol grafted chitosan to the glutaraldehyde in the step (5) is 100: 150-200.
Preferably, the atmosphere resistance furnace in step (6) comprises a calcining chamber and a base fixedly connected with the lower part of the inner part of the calcining chamber, a calcining crucible is arranged above the base, a rotating bearing is movably connected with the upper part of the atmosphere resistance furnace, an air inlet pipe is movably connected with the inner part of the rotating bearing, an air vent is arranged on the surface of the air inlet pipe, an air vent shaft is arranged below the air inlet pipe, and an air vent is arranged on the surface of the air vent shaft.
Preferably, the thermal activation process in the step (6) is an air atmosphere, the pressure in the atmosphere resistance furnace is 0.15-0.35MPa, and the thermal activation is carried out for 4-6h at 150-180 ℃.
Preferably, the high-temperature carbonization process in the step (6) is a thermal cracking process at 850 ℃ for 2-3h in a nitrogen atmosphere at 750-.
Preferably, the mass ratio of the pore-size and porosity adjustable nitrogen-doped porous carbon to the sublimed sulfur in the step (7) is 10: 20-35.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the nitrogen-doped porous carbon anode material with adjustable pore diameter and porosity is prepared by reacting polyethylene glycols with different molecular weights and molecular chain lengths to obtain single azido polyethylene glycols with different molecular weights and molecular chain lengths, wherein part of amino groups of carboxymethyl chitosan are subjected to nucleophilic substitution reaction with bromine atoms of bromopropyne in a sodium hydroxide alkaline system to obtain chitosan with alkynyl-containing side chains, and in a copper sulfate and sodium ascorbate click reaction catalytic system, the alkynyl-containing side chains of the chitosan and the azido groups of the single azido polyethylene glycols are subjected to 1,3 dipolar cycloaddition reaction to generate 1,2, 3-triazazole groups, so that the polyethylene glycols are grafted to the molecular chains of the chitosan in a covalent manner, and are highly dispersed in a cross-linked chitosan matrix through covalent bonding.
The nitrogen-doped porous carbon anode material with adjustable pore diameter and porosity forms a large amount of highly dispersed mesoporous and pore structures in a cross-linked chitosan matrix due to poor thermal stability of polyethylene glycol and thermal cracking gasification escape in a thermal activation process under certain pressure, and is further carbonized at high temperature, 1,2, 3-triazole groups are on a nitrogen source to obtain nitrogen-doped porous carbon, the size and the pore structure of the mesoporous are controlled by regulating the molecular weight and the molecular chain length of the polyethylene glycol, the smaller the molecular weight of the polyethylene glycol is, the smaller the size and the pore structure of the mesoporous are, the richer the pore structure is, so that the nitrogen-doped porous carbon with adjustable pore diameter and porosity is obtained and is further compounded with a sulfur simple substance, the rich pore structure of the nitrogen-doped porous carbon has a large amount of active adsorption sites, and has good chemical adsorption effect on polysulfide generated in a charging and discharging process, the loss of active sulfur substances is avoided, the active sulfur substances are dissolved in electrolyte, the shuttle effect is obviously reduced, the nitrogen-doped porous carbon provides a buffer layer for the volume expansion of the sulfur positive electrode, the circulation stability of the positive electrode material is improved, meanwhile, the nitrogen-doped porous carbon has excellent conductivity, and forms a three-dimensional conductive network with the active sulfur, so that the transmission and diffusion of electrons are promoted, and the positive electrode material has ultrahigh actual specific capacity and excellent electrochemical circulation stability under the synergistic effect.
Drawings
FIG. 1 is a schematic front view of an atmospheric resistance furnace;
FIG. 2 is a schematic side view of a bearing;
FIG. 3 is a partially enlarged schematic view of the intake pipe;
fig. 4 is a schematic vent adjustment.
1-atmosphere resistance furnace; 2-a calcining chamber; 3-a base; 4-calcining the crucible; 5-a bearing; 6, an air inlet pipe; 7-a vent hole; 8-a gas hole shaft; 9-air hole.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a nitrogen-doped porous carbon cathode material with adjustable pore diameter and porosity is prepared by the following steps:
(1) adding a toluene solvent, polyethylene glycol with molecular weight of 1000-6000 and triethylamine into a reaction bottle, stirring and dissolving, then slowly adding a toluene solution of p-toluenesulfonyl chloride, wherein the mass ratio of light polyethylene glycol to triethylamine to p-toluenesulfonyl chloride is 100:3-20:1.5-10, stirring at a constant speed at room temperature for 12-24h, carrying out reduced pressure distillation to remove the solvent, carrying out column chromatography separation and purification, and eluting with dichloromethane and methanol at a ratio of 5-10:1 to obtain the monosulfonyl polyethylene glycol.
(2) Adding N, N-dimethylformamide solvent, monosulfonyl polyethylene glycol and sodium azide in a mass ratio of 100:2-12 into a reaction bottle, heating to 80-110 ℃, stirring at a constant speed, refluxing for reaction for 30-40h, adding distilled water and dichloromethane for extraction, removing an organic phase, and drying to obtain the monosulfonyl polyethylene glycol.
(3) Adding a sodium hydroxide aqueous solution and an isopropanol solvent into a reaction bottle, adding carboxymethyl chitosan, performing ultrasonic dispersion uniformly, adding bromopropyne, heating to 65-75 ℃ at a mass ratio of 10:20-30, performing uniform stirring reaction for 4-8h, dropwise adding dilute hydrochloric acid to adjust the pH value to be neutral, adding an acetone solvent until a large amount of precipitate is separated out, filtering the solvent, washing with ethanol, and drying to prepare the chitosan with side chains containing alkynyl.
(4) Adding a distilled water solvent and chitosan with alkynyl side chains into a reaction bottle, adding copper sulfate, sodium ascorbate and single azido polyethylene glycol after ultrasonic dispersion is uniform, stirring at a constant speed for reaction for 20-40h, removing the solvent by reduced pressure distillation, and dialyzing and purifying a solid product to prepare the polyethylene glycol grafted chitosan, wherein the mass ratio of the copper sulfate, the sodium ascorbate and the single azido polyethylene glycol is 100:0.8-1.2:12-15:100 and 600.
(5) Adding distilled water solvent, polyethylene glycol grafted chitosan with the mass ratio of 100: 150-.
(6) Placing polyethylene glycol grafted crosslinked chitosan in an atmosphere resistance furnace, wherein the atmosphere resistance furnace comprises a calcining chamber, a base is fixedly connected below the inner part of the calcining chamber, a calcining crucible is arranged above the base, a rotating bearing is movably connected above the atmosphere resistance furnace, an air inlet pipe is movably connected inside the rotating bearing, a vent hole is arranged on the surface of the air inlet pipe, an air hole shaft is arranged below the air inlet pipe, an air hole is arranged on the surface of the air hole shaft, the pressure in the atmosphere resistance furnace is 0.15-0.35MPa, the heat activation process is carried out for 4-6h at the temperature of 150 ℃ -.
(7) Uniformly mixing nitrogen-doped porous carbon with adjustable aperture and porosity according to the mass ratio of 10:20-35 with sublimed sulfur, placing the mixture in a reaction kettle, heating to 160 ℃ for heat treatment at 150-.
Example 1
(1) Adding a toluene solvent, polyethylene glycol with the molecular weight of 1000 and triethylamine into a reaction bottle, stirring and dissolving, then slowly adding a toluene solution of p-toluenesulfonyl chloride, wherein the mass ratio of light polyethylene glycol to triethylamine to p-toluenesulfonyl chloride is 100:3:1.5, stirring at a constant speed at room temperature for 12 hours, distilling under reduced pressure to remove the solvent, and separating and purifying by column chromatography, wherein an eluent is dichloromethane and methanol which are 10:1, thereby preparing the monosulfonyl polyethylene glycol.
(2) Adding N, N-dimethylformamide solvent, monosulfonyl polyethylene glycol and sodium azide in a mass ratio of 100:2 into a reaction bottle, heating to 80 ℃, stirring at a constant speed, refluxing for reaction for 30 hours, adding distilled water and dichloromethane for extraction, removing an organic phase, and drying to prepare the monosulfonyl polyethylene glycol.
(3) Adding a sodium hydroxide aqueous solution and an isopropanol solvent into a reaction bottle, adding carboxymethyl chitosan, performing ultrasonic dispersion uniformly, adding bromopropyne, heating the mixture to 65 ℃ at a mass ratio of 10:20, stirring at a constant speed for reaction for 4 hours, dropwise adding dilute hydrochloric acid to adjust the pH value of the solution to be neutral, adding an acetone solvent until a large amount of precipitate is separated out, filtering the solvent, washing with ethanol, and drying to prepare the chitosan with side chains containing alkynyl.
(4) Adding a distilled water solvent and chitosan with alkynyl side chains into a reaction bottle, uniformly dispersing by ultrasonic, adding copper sulfate, sodium ascorbate and mono-azido polyethylene glycol in a mass ratio of 100:0.8:12:100, uniformly stirring for reaction for 20 hours, removing the solvent by reduced pressure distillation, dialyzing and purifying a solid product, and thus obtaining the polyethylene glycol grafted chitosan.
(5) Adding distilled water solvent, polyethylene glycol grafted chitosan and glutaraldehyde in a mass ratio of 100:150 into a reaction bottle, heating to 40 ℃, uniformly stirring for reaction for 12 hours, distilling under reduced pressure to remove the solvent, washing with ethanol and drying to prepare the polyethylene glycol grafted crosslinked chitosan.
(6) Placing polyethylene glycol grafted crosslinked chitosan into an atmosphere resistance furnace, wherein the atmosphere resistance furnace comprises a calcining chamber, a base is fixedly connected to the lower portion of the inner portion of the calcining chamber, a calcining crucible is arranged above the base, a rotating bearing is movably connected to the upper portion of the atmosphere resistance furnace, an air inlet pipe is movably connected to the inner portion of the rotating bearing, air holes are formed in the surface of the air inlet pipe, an air hole shaft is arranged below the air inlet pipe, air holes are formed in the surface of the air hole shaft and are used for air atmosphere, the pressure in the atmosphere resistance furnace is 0.15MPa, the heat activation process is carried out for 4 hours at 180 ℃, then in the nitrogen atmosphere, the temperature is raised to 750 ℃ for carrying out the high-temperature carbonization process for 2.
(7) Uniformly mixing nitrogen-doped porous carbon with adjustable aperture and porosity according to the mass ratio of 10:20 with sublimed sulfur, placing the mixture in a reaction kettle, heating the mixture to 150 ℃, carrying out heat treatment for 10 hours, placing the mixed product in an atmosphere resistance furnace, and carrying out heat treatment for 1 hour at 190 ℃ in a nitrogen atmosphere to prepare the nitrogen-doped porous carbon cathode material 1 with adjustable aperture and porosity.
Example 2
(1) Adding a toluene solvent, polyethylene glycol with molecular weight of 2000 and triethylamine into a reaction bottle, stirring and dissolving, then slowly adding a toluene solution of p-toluenesulfonyl chloride, wherein the mass ratio of light polyethylene glycol to triethylamine to p-toluenesulfonyl chloride is 100:6:3, stirring at a constant speed at room temperature for 24 hours, distilling under reduced pressure to remove the solvent, and separating and purifying by column chromatography, wherein an eluent is dichloromethane and methanol is 8:1, so as to prepare the monosulfonyl polyethylene glycol.
(2) Adding N, N-dimethylformamide solvent, monosulfonyl polyethylene glycol and sodium azide in a mass ratio of 100:5 into a reaction bottle, heating to 110 ℃, stirring at a constant speed, refluxing for reaction for 35 hours, adding distilled water and dichloromethane for extraction, removing an organic phase, and drying to prepare the monosulfonyl polyethylene glycol.
(3) Adding a sodium hydroxide aqueous solution and an isopropanol solvent into a reaction bottle, adding carboxymethyl chitosan, performing ultrasonic dispersion uniformly, adding bromopropyne, heating the mixture to 75 ℃ at a mass ratio of 10:23, stirring at a constant speed for reaction for 6 hours, dropwise adding dilute hydrochloric acid to adjust the pH value of the solution to be neutral, adding an acetone solvent until a large amount of precipitate is separated out, filtering the solvent, washing with ethanol, and drying to prepare the chitosan with side chains containing alkynyl.
(4) Adding a distilled water solvent and chitosan with alkynyl side chains into a reaction bottle, uniformly dispersing by ultrasonic, adding copper sulfate, sodium ascorbate and mono-azido polyethylene glycol in a mass ratio of 100:0.9:13:200, reacting for 40h under uniform stirring, removing the solvent by reduced pressure distillation, and dialyzing and purifying a solid product to obtain the polyethylene glycol grafted chitosan.
(5) Adding distilled water solvent, polyethylene glycol grafted chitosan and glutaraldehyde in a mass ratio of 100:160 into a reaction bottle, heating to 60 ℃, uniformly stirring for reaction for 12 hours, distilling under reduced pressure to remove the solvent, washing with ethanol and drying to prepare the polyethylene glycol grafted crosslinked chitosan.
(6) Placing polyethylene glycol grafted crosslinked chitosan into an atmosphere resistance furnace, wherein the atmosphere resistance furnace comprises a calcining chamber, a base is fixedly connected to the lower portion of the inner portion of the calcining chamber, a calcining crucible is arranged above the base, a rotating bearing is movably connected to the upper portion of the atmosphere resistance furnace, an air inlet pipe is movably connected to the inner portion of the rotating bearing, air holes are formed in the surface of the air inlet pipe, an air hole shaft is arranged below the air inlet pipe, air holes are formed in the surface of the air hole shaft and are used for air atmosphere, the pressure in the atmosphere resistance furnace is 0.35MPa, the heat activation process is carried out for 5 hours at 160 ℃, then in the nitrogen atmosphere, the temperature is raised to 820 ℃ for carrying out the high-temperature carbonization process for 3.
(7) Uniformly mixing nitrogen-doped porous carbon with adjustable aperture and porosity according to the mass ratio of 10:25 with sublimed sulfur, placing the mixture in a reaction kettle, heating the mixture to 160 ℃, carrying out heat treatment for 15 hours, placing the mixed product in an atmosphere resistance furnace, and carrying out heat treatment for 2 hours at 200 ℃ in a nitrogen atmosphere to prepare the nitrogen-doped porous carbon cathode material 2 with adjustable aperture and porosity.
Example 3
(1) Adding a toluene solvent, polyethylene glycol with the molecular weight of 4000 and triethylamine into a reaction bottle, stirring and dissolving, then slowly adding a toluene solution of p-toluenesulfonyl chloride, wherein the mass ratio of light polyethylene glycol to triethylamine to p-toluenesulfonyl chloride is 100:12:6, stirring at a constant speed at room temperature for 18h, distilling under reduced pressure to remove the solvent, and separating and purifying by column chromatography, wherein an eluent is dichloromethane and methanol is 8:1, so as to prepare the monosulfonyl polyethylene glycol.
(2) Adding N, N-dimethylformamide solvent, monosulfonyl polyethylene glycol and sodium azide in a mass ratio of 100:8 into a reaction bottle, heating to 100 ℃, stirring at a constant speed, refluxing for reaction for 35 hours, adding distilled water and dichloromethane for extraction, removing an organic phase, and drying to prepare the monosulfonyl polyethylene glycol.
(3) Adding a sodium hydroxide aqueous solution and an isopropanol solvent into a reaction bottle, adding carboxymethyl chitosan, performing ultrasonic dispersion uniformly, adding bromopropyne, heating the mixture to 70 ℃ at a mass ratio of 10:27, stirring at a constant speed for reaction for 6 hours, dropwise adding dilute hydrochloric acid to adjust the pH value of the solution to be neutral, adding an acetone solvent until a large amount of precipitate is separated out, filtering the solvent, washing with ethanol, and drying to prepare the chitosan with side chains containing alkynyl.
(4) Adding a distilled water solvent and side chain alkynyl-containing chitosan into a reaction bottle, uniformly dispersing by ultrasonic, adding copper sulfate, sodium ascorbate and single azido polyethylene glycol in a mass ratio of 100:1:13:400, uniformly stirring for reaction for 30h, distilling under reduced pressure to remove the solvent, and dialyzing and purifying a solid product to obtain the polyethylene glycol grafted chitosan.
(5) Adding distilled water solvent, polyethylene glycol grafted chitosan and glutaraldehyde in a mass ratio of 100:180 into a reaction bottle, heating to 50 ℃, uniformly stirring for reacting for 18 hours, distilling under reduced pressure to remove the solvent, washing with ethanol and drying to prepare the polyethylene glycol grafted crosslinked chitosan.
(6) Placing polyethylene glycol grafted crosslinked chitosan into an atmosphere resistance furnace, wherein the atmosphere resistance furnace comprises a calcining chamber, a base is fixedly connected to the lower portion of the inner portion of the calcining chamber, a calcining crucible is arranged above the base, a rotating bearing is movably connected to the upper portion of the atmosphere resistance furnace, an air inlet pipe is movably connected to the inner portion of the rotating bearing, air holes are formed in the surface of the air inlet pipe, an air hole shaft is arranged below the air inlet pipe, air holes are formed in the surface of the air hole shaft and are used for air atmosphere, the pressure in the atmosphere resistance furnace is 0.25MPa, the heat activation process is carried out for 5 hours at 170 ℃, then in the nitrogen atmosphere, the temperature is raised to 800 ℃ for carrying out the high-temperature carbonization process for 2.5.
(7) Uniformly mixing nitrogen-doped porous carbon with adjustable aperture and porosity according to the mass ratio of 10:30 with sublimed sulfur, placing the mixture in a reaction kettle, heating to 155 ℃, carrying out heat treatment for 12 hours, placing the mixed product in an atmosphere resistance furnace, and carrying out heat treatment for 1.5 hours at 195 ℃ in a nitrogen atmosphere to prepare the nitrogen-doped porous carbon cathode material 3 with adjustable aperture and porosity.
Example 4
(1) Adding a toluene solvent, polyethylene glycol with molecular weight of 6000 and triethylamine into a reaction bottle, stirring and dissolving, then slowly adding a toluene solution of p-toluenesulfonyl chloride, wherein the mass ratio of light polyethylene glycol to triethylamine to p-toluenesulfonyl chloride is 100:20:10, stirring at a constant speed for reaction for 24h at room temperature, distilling under reduced pressure to remove the solvent, and separating and purifying by column chromatography, wherein an eluent is dichloromethane and methanol is 5:1, so as to prepare the monosulfonyl polyethylene glycol.
(2) Adding N, N-dimethylformamide solvent, monosulfonyl polyethylene glycol and sodium azide in a mass ratio of 100:12 into a reaction bottle, heating to 110 ℃, stirring at a constant speed, refluxing for 40 hours, adding distilled water and dichloromethane for extraction, removing an organic phase, and drying to prepare the monosulfonyl polyethylene glycol.
(3) Adding a sodium hydroxide aqueous solution and an isopropanol solvent into a reaction bottle, adding carboxymethyl chitosan, performing ultrasonic dispersion uniformly, adding bromopropyne, heating the mixture to 75 ℃ at a mass ratio of 10:30, stirring at a constant speed for reaction for 8 hours, dropwise adding dilute hydrochloric acid to adjust the pH of the solution to be neutral, adding an acetone solvent until a large amount of precipitate is separated out, filtering the solvent, washing with ethanol, and drying to prepare the chitosan with side chains containing alkynyl.
(4) Adding a distilled water solvent and side chain alkynyl-containing chitosan into a reaction bottle, uniformly dispersing by ultrasonic, adding copper sulfate, sodium ascorbate and single azido polyethylene glycol in a mass ratio of 100:1.2:15:600, uniformly stirring for reaction for 40 hours, removing the solvent by reduced pressure distillation, dialyzing and purifying a solid product, and preparing the polyethylene glycol grafted chitosan.
(5) Adding distilled water solvent, polyethylene glycol grafted chitosan and glutaraldehyde in a mass ratio of 100:200 into a reaction bottle, heating to 60 ℃, uniformly stirring for reaction for 24 hours, distilling under reduced pressure to remove the solvent, washing with ethanol, and drying to prepare the polyethylene glycol grafted crosslinked chitosan.
(6) Placing polyethylene glycol grafted crosslinked chitosan into an atmosphere resistance furnace, wherein the atmosphere resistance furnace comprises a calcining chamber, a base is fixedly connected to the lower portion of the inner portion of the calcining chamber, a calcining crucible is arranged above the base, a rotating bearing is movably connected to the upper portion of the atmosphere resistance furnace, an air inlet pipe is movably connected to the inner portion of the rotating bearing, air holes are formed in the surface of the air inlet pipe, an air hole shaft is arranged below the air inlet pipe, air holes are formed in the surface of the air hole shaft and are used for air atmosphere, the pressure in the atmosphere resistance furnace is 0.35MPa, the heat activation process is carried out for 6 hours at 180 ℃, then in the nitrogen atmosphere, the temperature is raised to 850 ℃ for carrying out the high-temperature carbonization process for 3.
(7) Uniformly mixing nitrogen-doped porous carbon with adjustable aperture and porosity according to the mass ratio of 10:35 with sublimed sulfur, placing the mixture in a reaction kettle, heating the mixture to 160 ℃, carrying out heat treatment for 15 hours, placing the mixed product in an atmosphere resistance furnace, and carrying out heat treatment for 2 hours at 200 ℃ in a nitrogen atmosphere to prepare the nitrogen-doped porous carbon anode material 4 with adjustable aperture and porosity.
Comparative example 1
(1) Adding a toluene solvent, polyethylene glycol with the molecular weight of 4000 and triethylamine into a reaction bottle, stirring and dissolving, then slowly adding a toluene solution of p-toluenesulfonyl chloride, wherein the mass ratio of light polyethylene glycol to triethylamine to p-toluenesulfonyl chloride is 100:12:6, stirring at a constant speed at room temperature for 24 hours, distilling under reduced pressure to remove the solvent, and separating and purifying by column chromatography, wherein an eluent is dichloromethane and methanol is 8:1, so as to prepare the monosulfonyl polyethylene glycol.
(2) Adding N, N-dimethylformamide solvent, monosulfonyl polyethylene glycol and sodium azide in a mass ratio of 100:8 into a reaction bottle, heating to 110 ℃, stirring at a constant speed, refluxing for 40 hours, adding distilled water and dichloromethane for extraction, removing an organic phase, and drying to prepare the monosulfonyl polyethylene glycol.
(3) Adding a sodium hydroxide aqueous solution and an isopropanol solvent into a reaction bottle, adding carboxymethyl chitosan, performing ultrasonic dispersion uniformly, adding bromopropyne, heating the mixture to 75 ℃ at a mass ratio of 10:18, stirring at a constant speed for reaction for 8 hours, dropwise adding dilute hydrochloric acid to adjust the pH of the solution to be neutral, adding an acetone solvent until a large amount of precipitate is separated out, filtering the solvent, washing with ethanol, and drying to prepare the chitosan with side chains containing alkynyl.
(4) Adding a distilled water solvent and side chain alkynyl-containing chitosan into a reaction bottle, uniformly dispersing by ultrasonic, adding copper sulfate, sodium ascorbate and single azido polyethylene glycol at a mass ratio of 100:0.7:10:60, uniformly stirring for reaction for 40 hours, removing the solvent by reduced pressure distillation, dialyzing and purifying a solid product, and preparing the polyethylene glycol grafted chitosan.
(5) Adding distilled water solvent, polyethylene glycol grafted chitosan and glutaraldehyde in a mass ratio of 100:120 into a reaction bottle, heating to 40 ℃, uniformly stirring for reaction for 24 hours, distilling under reduced pressure to remove the solvent, washing with ethanol, and drying to prepare the polyethylene glycol grafted crosslinked chitosan.
(6) Placing polyethylene glycol grafted crosslinked chitosan into an atmosphere resistance furnace, wherein the atmosphere resistance furnace comprises a calcining chamber, a base is fixedly connected to the lower portion of the inner portion of the calcining chamber, a calcining crucible is arranged above the base, a rotating bearing is movably connected to the upper portion of the atmosphere resistance furnace, an air inlet pipe is movably connected to the inner portion of the rotating bearing, air holes are formed in the surface of the air inlet pipe, an air hole shaft is arranged below the air inlet pipe, air holes are formed in the surface of the air hole shaft and are used for air atmosphere, the pressure in the atmosphere resistance furnace is 0.25MPa, the heat activation process is carried out for 6 hours at 180 ℃, then in the nitrogen atmosphere, the temperature is raised to 850 ℃ for carrying out the high-temperature carbonization process for 3.
(7) Uniformly mixing nitrogen-doped porous carbon with adjustable aperture and porosity according to the mass ratio of 10:15 with sublimed sulfur, placing the mixture in a reaction kettle, heating the mixture to 160 ℃, carrying out heat treatment for 15 hours, placing the mixed product in an atmosphere resistance furnace, and carrying out heat treatment for 1 hour at 200 ℃ in a nitrogen atmosphere to prepare a nitrogen-doped porous carbon positive material with adjustable aperture and porosity, wherein the comparison ratio is 1.
The nitrogen-doped porous carbon anode material with adjustable pore diameter and porosity in the examples and the comparative examples is mixed with acetylene black and polyvinylidene fluoride to prepare slurry, the slurry is coated on the surface of aluminum foil to prepare the working anode of the lithium-sulfur battery, a lithium sheet is taken as a cathode, 1mol/L lithium bistrifluoromethylsulfonyl imide +1, 3-dioxolane + ethylene glycol dimethyl ether solution is taken as electrolyte, the CR2025 type battery is assembled in argon atmosphere, and electrochemical performance tests are carried out in a CT-4008-5V-10Ma-164 type battery detection system and a CHI760D electrochemical workstation, wherein the test standard is GB/T36276 + 2018.
Claims (9)
1. The utility model provides a nitrogen doping porous carbon cathode material with adjustable aperture and porosity which characterized in that: the preparation method of the nitrogen-doped porous carbon cathode material with adjustable aperture and porosity comprises the following steps:
(1) adding polyethylene glycol, triethylamine and p-toluenesulfonyl chloride into a toluene solvent, and reacting at room temperature for 12-24h to prepare monosulfonyl polyethylene glycol;
(2) adding monosulfonyl polyethylene glycol and sodium azide in a mass ratio of 100:2-12 into an N, N-dimethylformamide solvent, heating to 80-110 ℃, and reacting for 30-40h to prepare the monosulfonyl polyethylene glycol;
(3) adding an isopropanol solvent into a sodium hydroxide aqueous solution, adding carboxymethyl chitosan, uniformly dispersing by using ultrasonic waves, adding bromopropyne, heating to 65-75 ℃, and reacting for 4-8 hours to prepare chitosan with side chains containing alkynyl;
(4) adding side chain alkynyl-containing chitosan into a distilled aqueous solvent, adding copper sulfate, sodium ascorbate and single azido polyethylene glycol after uniform ultrasonic dispersion, and reacting for 20-40h to prepare polyethylene glycol grafted chitosan;
(5) adding polyethylene glycol grafted chitosan and glutaraldehyde into a distilled water solvent, heating to 40-60 ℃, and reacting for 12-24h to prepare polyethylene glycol grafted crosslinked chitosan;
(6) placing the polyethylene glycol grafted crosslinked chitosan in an atmosphere resistance furnace to perform a thermal activation process and a high-temperature carbonization process to prepare nitrogen-doped porous carbon with adjustable aperture and porosity;
(7) uniformly mixing the nitrogen-doped porous carbon with adjustable aperture and porosity with sublimed sulfur, placing the mixture in a reaction kettle, heating the mixture to 160 ℃, carrying out heat treatment for 10-15h, placing the mixed product in an atmosphere resistance furnace, and carrying out heat treatment for 1-2h at 200 ℃ in the nitrogen atmosphere to prepare the nitrogen-doped porous carbon anode material with adjustable aperture and porosity.
2. The pore size and porosity adjustable nitrogen doped porous carbon cathode material according to claim 1, characterized in that: the molecular weight of the polyethylene glycol in the step (1) is 1000-6000, and the mass ratio of the polyethylene glycol to the triethylamine to the p-toluenesulfonyl chloride is 100:3-20: 1.5-10.
3. The pore size and porosity adjustable nitrogen doped porous carbon cathode material according to claim 1, characterized in that: the mass ratio of the carboxymethyl chitosan to the bromopropyne in the step (3) is 10: 20-30.
4. The pore size and porosity adjustable nitrogen doped porous carbon cathode material according to claim 1, characterized in that: the mass ratio of the side chain containing alkynyl chitosan, copper sulfate, sodium ascorbate and mono-azido polyethylene glycol in the step (4) is 100:0.8-1.2:12-15: 100-.
5. The pore size and porosity adjustable nitrogen doped porous carbon cathode material according to claim 1, characterized in that: the mass ratio of the polyethylene glycol grafted chitosan to the glutaraldehyde in the step (5) is 100: 150-200.
6. The pore size and porosity adjustable nitrogen doped porous carbon cathode material according to claim 1, characterized in that: the atmosphere resistance furnace in step (6) includes calcining chamber, the inside below fixedly connected with base of calcining chamber, and the base top is provided with the calcining crucible, and atmosphere resistance furnace top swing joint has rolling bearing, and the inside swing joint of rolling bearing has the intake pipe, and the intake pipe surface is provided with the air vent, and the intake pipe below is provided with the gas vent axle, and gas vent axle surface is provided with the gas vent.
7. The pore size and porosity adjustable nitrogen doped porous carbon cathode material according to claim 1, characterized in that: the thermal activation process in the step (6) is air atmosphere, the pressure in the atmosphere resistance furnace is 0.15-0.35MPa, and the thermal activation is carried out for 4-6h at the temperature of 150-180 ℃.
8. The pore size and porosity adjustable nitrogen doped porous carbon cathode material according to claim 1, characterized in that: the high-temperature carbonization process in the step (6) is thermal cracking for 2-3h at the temperature of 750-850 ℃ in a nitrogen atmosphere.
9. The pore size and porosity adjustable nitrogen doped porous carbon cathode material according to claim 1, characterized in that: the mass ratio of the nitrogen-doped porous carbon with adjustable pore diameter and porosity in the step (7) to the sublimed sulfur is 10: 20-35.
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