CN105776170A - Method for preparing lumpy nitrogenous multistage-pore-passage charcoal material - Google Patents
Method for preparing lumpy nitrogenous multistage-pore-passage charcoal material Download PDFInfo
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- CN105776170A CN105776170A CN201410779656.8A CN201410779656A CN105776170A CN 105776170 A CN105776170 A CN 105776170A CN 201410779656 A CN201410779656 A CN 201410779656A CN 105776170 A CN105776170 A CN 105776170A
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Abstract
The invention relates to a method for preparing polyacrylonitrile-based lumpy nitrogenous porous charcoal. The method comprises the steps: taking polyacrylonitrile as a precursor, taking DMF, DMSO or DMSO/water as a solvent, and preparing a polyacrylonitrile-based lumpy polymer by a stable-system sol-gel process by using a hydrogen bonding action between polyacrylonitrile and a silicon source hydrolyzate, i.e., silicic acid obtained under base catalysis; and putting the polyacrylonitrile-based lumpy polymer in a charring furnace, carrying out charring under the protection of an inert atmosphere, and removing SiO2, thereby obtaining a lumpy nitrogenous multistage-pore-passage-structured charcoal material. According to the method disclosed by the invention, the preparation method is simple in operation, the equipment is simple, the conventional method that polyacrylonitrile-based charcoal materials are produced by electrostatic spinning is broken through, and the nitrogenous multistage-pore charcoal material with lumpy morphology and an adjustable pore passage structure can be prepared.
Description
Technical field
The preparation method that the present invention relates to a kind of nitrogenous porous carbon material of polyacrylonitrile-radical block, utilize this process can the structural nitrogenous multistage pore canal Carbon Materials of synthesizing block, belong to novel Heteroatom doping carbon material preparation and application of electrode field.
Background technology
Porous charcoal is within the scope of the space scales such as nano-micrometre, there is the porous carbonaceous material of ultramicron and superficiality solid property, self there is abundant pore passage structure and surface chemical structure characteristic, show good application prospect in fields such as adsorbing material, catalyst carrier and electrode materials.
In electrode material application, research thinks that foramen magnum-mesoporous-micropore tandem type multi-stage porous block structure Carbon Materials can be effectively improved the ion transportation of electrode.It is long that the preparation method of the multilevel hole material of current report is generally subjected to synthesis cycle；Special technological requirement (CO2Supercritical drying etc.)；Needing to consume a large amount of solvent, environment is unfriendly waits restriction." nanometer casting " is the effective ways that a class prepares multi-stage porous block structure material, generally includes: the preparation of multi-stage porous block template；Charcoal source dipping and the polymerization in pattern hole；Control carbonization；Remove the steps such as template.Although the method can prepare the multi-stage porous block structure material having ad hoc structure with pattern effectively, but loaded down with trivial details preparation process limits its scale application.Therefore, a kind of simple efficient preparation method of development is particularly necessary.By the chemical action between template presoma and charcoal source, reaction in-situ one step is utilized to obtain the composite construction of charcoal and template, it is possible to efficiently and rapidly to prepare porous blocks structure Carbon Materials.
The surface chemical property of Carbon Materials affects the performance in its application of electrode field, and usual people adopt post processing mode to introduce nitrogen-containing functional group in Carbon Materials, as by ammonia high-temperature activation porous carbon material, prepared nitrogenous porous carbon material.The content that post processing mode introduces nitrogen-containing functional group in charcoal skeleton is relatively low, and nitrogen-containing functional group is distributed only over the surface of Carbon Materials, and distribution uniformity is poor.Owing to a large amount of toxic gas used in Carbon Materials processing procedure, making this preparation process not environment friendly.By post processing mode while the nitrogenous hat of carbon surface introducing can be rolled into a ball, also the original pore passage structure of Carbon Materials and pattern can be caused certain destruction.This method preparation condition controllability is relatively poor, and the hetero atom of introducing is also poor at the surface distribution uniformity of Carbon Materials.Therefore need the simple synthesis technique of development badly, to synthesize the modified porous blocks Carbon Materials of hetero atom for target, simplify preparation method.
Polyacrylonitrile is a kind of organic high molecular polymer with abundant nitrogen-containing functional group, is widely used in the fields such as industrial electrostatic spinning, for preparing various nitrogenous Carbon fibe material.This kind of Carbon fibe material processing conditions requires higher, and process route is more complicated, and the powder structure moulding process of Carbon fibe material is more complicated, and powder morphology also limit it and is difficult to have higher mass transfer rate.By comparison, the Carbon Materials of block structure, there is through three-dimensional multistage pore passage structure, show quick mass transfer rate and good shaping characteristic.Thus how can use simple synthesizing mean, and utilize this abundant raw material of industry of polyacrylonitrile, preparing the multi-stage artery structure block Carbon Materials of the nitrogen-containing functional group with high degree of dispersion is problem currently to be solved.
Summary of the invention
It is an object of the invention to provide a kind of preparation method that can prepare the nitrogenous multi-stage artery structure block Carbon Materials of polyacrylonitrile-radical.
In order to achieve the above object, the present invention adopts the following technical scheme that with polyacrylonitrile for raw material, in the sol system of base catalysis silicon source hydrolysis, by the hydrogen bond action between polyacrylonitrile and silicon source hydrolyzate, form homogeneous polyacrylonitrile-silica alcosol compound system, prepare the adjustable nitrogenous loose structure block Carbon Materials of pore structure through stable sol-gel process.Block Carbon Materials prepared by this technology have through foramen magnum-mesoporous-micropore, containing abundant nitrogen-containing functional group, show modified surface chemical property.
A kind of preparation method of the nitrogenous multistage pore canal Carbon Materials of block, this preparation method step is as follows:
With polyacrylonitrile for charcoal source, it is dissolved in solvent, is configured to finite concentration polyacrylonitrile solution.Meanwhile, silicon source is dissolved in same solvent, stirs.Polyacrylonitrile solution is added in the solution of silicon source, stir.Adding catalyst solution at a certain temperature, stirring obtains homogeneous solution.By its aging certain time at a certain temperature, obtaining polymer gel, gel is dried.Again by polymer uniform temperature carbonization under row argon gas atmosphere, obtain block charcoal-silica composite.Adopt alkali liquor to be removed by the silicon oxide in block charcoal, namely obtain the nitrogenous porous carbon material of block.
In preparation method, the concentration of described polyacrylonitrile solution is 50gL-1～200gL-1, solvent for use is the one in DMF, DMSO or DMSO/ water.The mass ratio of silicon source and polyacrylonitrile is 0.2～2:1, and wherein silicon source is tetraethyl orthosilicate or sodium silicate.The consumption of modulation silicon source solution, the pore structure of Effective Regulation Carbon Materials and specific surface area.
In preparation method, described catalyst be N-Methylimidazole., lysine, ethylenediamine, 1, one in 6-hexamethylene diamine, aniline or ammonia, and it is configured to ethanol-water solution (mass ratio of second alcohol and water is 0.8～1.25:1), its concentration is 0.01gL-1～0.1gL-1.The mass ratio of silicon source and catalyst is 5～10:1.Controlling solid content is 5%～15%.
Described carbonization program adopts 800 DEG C of carbonization 2h.Described alkali silicon process, adopts the water of the sodium hydroxide of 8% and alcoholic solution (3:1 volume ratio) 50 DEG C to remove silicon 24h, then washes, 90 DEG C of dry 24h.The specific surface area of the described nitrogenous porous charcoal of polypropylene-base block is 200～500m2g-1。
Described multi-stage porous refers to the pore passage structure of foramen magnum-mesoporous-micropore series connection, and wherein macropore refers to greater than the duct of 50nm, and the mesoporous duct referring to 2～50nm, micropore is meant less than the duct of 2nm；The macropore with 7.5～9.5 μm of prepared Carbon Materials, macropore pore volume is 1.0～1.5cm3g-1, there is the mesoporous of 2～5nm, mesoporous pore volume is 0.2～0.4cm3g-1, there is the micropore of 0.4-0.8nm integrated distribution, Micropore volume is about 0.1～0.2cm3g-1；
The nitrogenous hierarchical porous structure Carbon Materials of gained block can be used for preparing the charcoal sulfur composite of lithium-sulfur cell sulfur positive pole.
The excellent part of the present invention is in that: with polyacrylonitrile as charcoal source precursor, by the hydrogen bond action between the silicon source hydrolyzate of polyacrylonitrile and base catalysis, and utilize the sol-gel process of stable system, prepare homogeneous charcoal-silica composite, and then obtain nitrogenous porous blocks charcoal.By the modulation to polyacrylonitrile Yu silicon source ratio, the three-dimensional multistage pore passage structure of Effective Regulation gained block Carbon Materials；Simultaneously as polyacrylonitrile has abundant nitrogen-containing functional group, by the cyclisation of cyano group in pyrolytic process Yu alkyl chain, it is possible to obtain have the three-dimensional multistage pore structure block Carbon Materials of abundant nitrogen-containing functional group.The present invention breaks through the thinking being prepared polypropylene-base Carbon fibe by electrostatic spinning technique of routine, obtains conveniently and efficiently and has the pore structural nitrogenous block Carbon Materials of three-dimensional multistage.Prepared Carbon Materials is applied in lithium sulfur battery anode material, it is possible to payload elemental sulfur, and has 1400mAhg under 0.1C electric current density-1Specific capacity, 50 times circulation after still there is 750mAhg-1Stable specific capacity.
Compared to existing technology, the invention has the beneficial effects as follows:
1. break through the method that electrostatic spinning prepares PAN based carbon fiber, based on the hydrogen bond action of polyacrylonitrile Yu silicon source hydrolyzate, utilize sol-gel process, prepare polyacrylonitrile-radical block Carbon Materials.This block structure Carbon Materials, has quick ion transportation, and can be processed into integral electrodes, it is to avoid the use of binding agent in application of electrode field, improves the electronic conductivity of electrode further.
2. regulation and control silicon source and the ratio of polyacrylonitrile, prepared foramen magnum-mesoporous-microcellular structure adjustable quickly and easily, has large hole and holds, and has the block body stephanoporate Carbon Materials of abundant nitrogen-containing functional group.
3. preparing charcoal-sulfur compound with the porous charcoal of present invention synthesis for carrier, as lithium sulfur battery anode material, first discharge specific capacity is 1400mAhg-1, under 0.1C electric current density, after 50 circulations, specific capacity reaches 750mAhg-1Above, there is good cyclical stability and good application prospect.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the nitrogenous multi-stage porous charcoal of the block structure prepared by the present invention；
Fig. 2 is the N2 adsorption curve chart of the nitrogenous multi-stage porous charcoal of the block structure prepared by the present invention；
Fig. 3 is the lithium-sulfur cell performance map of the nitrogenous multi-stage porous charcoal of the block structure prepared by the present invention.
Detailed description of the invention
The following examples can make those of ordinary skill in the art more fully understand the present invention, but does not limit the present invention in any form.
Embodiment 1
Take 1ml tetraethyl orthosilicate (TEOS) and be dissolved in 3mlDMF, be uniformly mixing to obtain colourless transparent solution, meanwhile, prepare 125gL-1Polyacrylonitrile-DMF solution 1.5ml, and add it to, in TEOS-DMF solution, stir.Under 80 DEG C of stirring states, add 1, the 6-hexamethylene diamine solution second alcohol and water of 1:1 (solvent be) of 0.01728g, stir.Reaction system is sealed, proceeds to 90 DEG C of aging 12h, obtain block polymer through super-dry.And by it under inert atmosphere protection, 3 DEG C of min-1It is warming up to 400 DEG C, constant temperature 60min, then it is warmed up to 800 DEG C with same heating rate, and constant temperature 120min, block charcoal-silica composite that form keeps can be obtained.The water and the alcoholic solution (3:1 volume ratio) 50 DEG C that adopt the sodium hydroxide of 8% remove silicon 24h, then 90 DEG C of dry 24h of washing.
The scanning electron microscope of this example gained block Carbon Materials is as shown in Figure 1.Sample have through foramen magnum-mesoporous-micropore, prepared multi-stage porous charcoal has the macropore of 7.5～9.5 μm, and macropore pore volume is 1.0cm3g-1, there is the mesoporous of 2～5nm, mesoporous pore volume is 0.24cm3g-1, there is the micropore of about 0.7nm integrated distribution, Micropore volume is about 0.12cm3g-1.The nitrogenous Carbon Materials of gained block multi-stage artery structure has 350.2m2g-1Specific surface area, Fig. 2 is its N2 adsorption curve.
Embodiment 2
Take 1.2ml tetraethyl orthosilicate (TEOS) and be dissolved in 3mlDMF, be uniformly mixing to obtain colourless transparent solution, meanwhile, prepare 100gL-1Polyacrylonitrile-DMF solution 5ml, and add it to, in TEOS-DMF solution, stir.Add 800ulNH3.H2O, stirs.Reaction system being sealed, proceed to aging 12h under uniform temperature, after natural cooling, carry out solvent displacement (ethanol replacement 3 times, normal hexane is replaced 3 times and trim,ethylchlorosilane is replaced 3 times), 50 DEG C obtain block polymer after drying.And by it under inert atmosphere protection, 3 DEG C of min-1It is warming up to 400 DEG C, constant temperature 60min, then it is warmed up to 800 DEG C with same heating rate, and constant temperature 120min, block charcoal-silica composite that form keeps can be obtained.The water and the alcoholic solution (3:1 volume ratio) 50 DEG C that adopt the sodium hydroxide of 8% remove silicon 24h, then 90 DEG C of dry 24h of washing.
Embodiment 3
The nitrogenous porous charcoal of block of Example 1 preparation, prepares into charcoal-sulfur compound that sulfur content is 44%.Being ground by charcoal-sulfur compound, acetylene black and PVDF 8:1:1 in mass ratio, after adding appropriate N-Methyl pyrrolidone mix homogeneously, on aluminium foil, pole piece is prepared in coating.By electrode slice (size 1cm × 1cm, about 25～50 μ m-thick, containing the sulfur of 0.5～1.5mg) as positive pole, lithium sheet, as negative pole, is assembled into button cell, and tests its chemical property under the multiplying power electric current density of 0.1C.Fig. 3 is the electrochemical cycle stability linearity curve of material.First discharge specific capacity is 1400mAhg-1, under 0.1C electric current density, after 50 circulations, specific capacity reaches 750mAhg-1Above, there is good cyclical stability.
Claims (10)
1. the preparation method of the nitrogenous multistage pore canal Carbon Materials of block, it is characterized in that: with polyacrylonitrile for raw material, polyacrylonitrile is by the effect of hydrogen bond, homogeneous polyacrylonitrile-silica alcosol system is formed with base catalysis silicon source hydrolyzate silicic acid, through aging prepared polyacrylonitrile-silica gel, prepare nitrogenous multi-stage porous block Carbon Materials then through high temperature pyrolysis and alkaline cleaning procedure after drying.
2. preparation method according to claim 1, it is characterized in that: concrete steps include: first polyacrylonitrile solution, silicon source solution, catalyst solution mixing are prepared colloidal sol, through aging, dry, after high temperature carbonization, remove silicon oxide with dipping by lye, prepare nitrogenous multi-stage artery structure block Carbon Materials.
3. preparation method according to claim 2, it is characterised in that: the molecular weight of polyacrylonitrile used is 50,000～200,000, and the concentration of the polyacrylonitrile in polyacrylonitrile solution is 50gL-1～200gL-1；Silicon source used can be the one in tetraethyl orthosilicate or sodium silicate or two kinds of mixture, and in the solution of silicon source, the concentration in silicon source is 0.15gL-1～0.5gL-1；Described catalyst can be N-Methylimidazole. or lysine or ethylenediamine or 1,6-hexamethylene diamine or aniline or ammonia；In catalyst solution, the concentration of catalyst is 0.01gL1～0.1gL-1。
4. the preparation method according to Claims 2 or 3, it is characterised in that: after mixing, in solution, the mass ratio of silicon source and polyacrylonitrile is 0.2～1:1；After mixing, in solution, the mass ratio of silicon source and catalyst is 1～10:1.
5. the preparation method according to Claims 2 or 3, it is characterised in that: the solvent that polyacrylonitrile solution, silicon source solution, catalyst solution adopt is dimethylformamide (DMF) or dimethyl sulfoxide (DMSO) or DMSO that volume ratio is 4～9:1 and water mixed solvent.
6. preparation method according to claim 1 and 2, it is characterised in that: controlling system solid content in the process of the prepared colloidal sol of mixing is 5%～15%.
7. preparation method according to claim 1 and 2, it is characterised in that: the temperature of burin-in process is 60 DEG C～100 DEG C, and the time is 4h～24h；The temperature of dried is 40 DEG C～60 DEG C, and the time is 24h～36h.
8. preparation method according to claim 1 and 2, it is characterised in that: carbonization program is 2～5 DEG C of min of employing-1Heating rate risen to 300 DEG C～400 DEG C constant temperature 60min～120min by room temperature, then be warming up to 500 DEG C～900 DEG C, constant temperature 60min～240min.
9. preparation method according to claim 1 and 2, it is characterised in that: alkali liquor is water and the alcoholic solution of sodium hydroxide, and the mass concentration of sodium hydroxide is 4%～16%；In the water of preparation alkali liquor and alcohol solvent, the volume ratio of water and ethanol is 3～6:1.
10. preparation method according to claim 1 and 2, it is characterised in that: described multi-stage porous refers to the pore passage structure of foramen magnum-mesoporous-micropore series connection, and the macropore with 7.5～9.5 μm of prepared Carbon Materials, macropore pore volume is 1.0～1.5cm3g-1, there is the mesoporous of 2～5nm, mesoporous pore volume is 0.2～0.4cm3g-1, there is the micropore of 0.4-0.8nm integrated distribution, Micropore volume is about 0.1～0.2cm3g-1；
The nitrogenous hierarchical porous structure Carbon Materials of gained block can be used for preparing the charcoal sulfur composite of lithium-sulfur cell sulfur positive pole.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108987648A (en) * | 2018-06-28 | 2018-12-11 | 肇庆市华师大光电产业研究院 | A kind of preparation method applied to the functional interlayer of anode in lithium-sulfur cell |
| CN109896513A (en) * | 2017-12-08 | 2019-06-18 | 中国科学院大连化学物理研究所 | A kind of preparation method of ion exchange resin base porous carbon material |
| CN109896512A (en) * | 2017-12-08 | 2019-06-18 | 中国科学院大连化学物理研究所 | A kind of method that low cost prepares ion exchange resin base porous carbon material |
| CN114644736A (en) * | 2022-03-15 | 2022-06-21 | 中山大学 | Porous carbon-based polymer brush and preparation method and application thereof |
| CN115650207A (en) * | 2022-12-22 | 2023-01-31 | 河北省科学院能源研究所 | Porous carbon material and preparation method and application thereof |
| CN116216874A (en) * | 2023-03-23 | 2023-06-06 | 重庆大学 | Water body restoration agent for controlling cyanobacteria bloom, preparation method and application |
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| CN109896513A (en) * | 2017-12-08 | 2019-06-18 | 中国科学院大连化学物理研究所 | A kind of preparation method of ion exchange resin base porous carbon material |
| CN109896512A (en) * | 2017-12-08 | 2019-06-18 | 中国科学院大连化学物理研究所 | A kind of method that low cost prepares ion exchange resin base porous carbon material |
| CN108987648A (en) * | 2018-06-28 | 2018-12-11 | 肇庆市华师大光电产业研究院 | A kind of preparation method applied to the functional interlayer of anode in lithium-sulfur cell |
| CN114644736A (en) * | 2022-03-15 | 2022-06-21 | 中山大学 | Porous carbon-based polymer brush and preparation method and application thereof |
| CN115650207A (en) * | 2022-12-22 | 2023-01-31 | 河北省科学院能源研究所 | Porous carbon material and preparation method and application thereof |
| CN116216874A (en) * | 2023-03-23 | 2023-06-06 | 重庆大学 | Water body restoration agent for controlling cyanobacteria bloom, preparation method and application |
| CN116216874B (en) * | 2023-03-23 | 2024-04-30 | 重庆大学 | Water body restoration agent for controlling cyanobacteria bloom, preparation method and application |
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