CN104891475B - A kind of room temperature preparation method of Heteroatom doping type carbon material - Google Patents
A kind of room temperature preparation method of Heteroatom doping type carbon material Download PDFInfo
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Abstract
The present invention relates to a kind of room temperature preparation method of Heteroatom doping type carbon material, it is comprised the following steps：Halogenated high-molecular-weight, highly basic and intensive polar solvent are mixed to get mixture, the mixture is ground at room temperature then, after grinding terminates, directly cleaned and dried, that is, obtain the Heteroatom doping type carbon material；Wherein described halogenated high-molecular-weight is polyvinylidene fluoride, polyvinylidene chloride or polyvinyl chloride；Wherein described highly basic is alkali (soil) metal hydroxides, alkali (soil) metal alkoxide, alkali (soil) metal sulfide, alkali (soil) metal amide or alkali (soil) metal nitride；Wherein described intensive polar solvent is N, N dimethylformamides, N, N dimethylacetylamides, dimethyl sulfoxide (DMSO) or N-methyl pyrrolidones；Wherein described room temperature is 10 40 DEG C.The method raw material are cheap and easily-available, simple to operate, safe, are easily applicable industry expanding production.
Description
Technical field
The invention belongs to the preparation method field of doping type graphitized carbon material.
Background technology
Carbon is one of element most closely related with human being's production life activity, and its multiple electronic orbital characteristics makes it
With abundant into bond hybridization form so that it to be turned into uniquely complete and is built from zero dimension fullerene to one with single-element
Dimension CNT arrives the element of three dimensional diamond and various porous carbon materials to two-dimensional graphene again.There are two kinds of simple substance at present
Carbon form fullerene and Graphene obtain the Nobel Prize of 1996 and 2010 respectively, it is sufficient to prove the important of carbon material research
Property.It is like a raging fire that the research of carbon material in recent years and corresponding production are carried out, and can look for the body of seeing carbon material in various fields
Shadow, this also causes that the preparation of carbon material has very important significance.
The method that at present prepared by existing many kinds carbon materials is seen in report, applied it is tactful can be rough be summarized as with
Under several aspects.(1) gaseous phase materials is reacted on base material in chemical vapor deposition, as reative cell and obtain thin layer
Carbon material, the strategy can be used to prepare Graphene of CNT, Graphene and three-dimensional etc..Carbon material prepared by the method
With structure higher and atom regularity, electricity aspect is can be applied to, but its scale is limited.(2) pyrolysismethod, i.e., directly add
Thermal response raw material, makes it polymerization occur in the case where high temperature energy is input into, reform and go function dough, finally give with compared with
The graphited carbon material in region of high carbon content, carbon material prepared by the strategy is generally amorphous carbon material, but with abundant
Pore passage structure and plasticity higher, but the shortcoming of the method is also more obvious, and such as controllability is compared to chemical vapour deposition technique
It is poor, it is that environmental protection considers, need strict tail gas exhaust to process during functional group is gone to.But this strategy can be fine
Be actual production place mat.But the preparation strategy of this two major class is required to energy input higher, is such as entered using high annealing
Row carbonization and graphitization.How to realize carbon material particularly adulterate carbon material low energy supply, low cost, low stain it is simple
Preparing has great science and practical significance.
Heteroatom doping type carbon material is prepared by simple Ginding process at room temperature the present invention provides one kind
New method.
The content of the invention
The invention provides a kind of room temperature preparation method of Heteroatom doping type carbon material, it is comprised the following steps：
Halogenated high-molecular-weight, highly basic and intensive polar solvent are mixed to get mixture, the mixture is entered at room temperature then
Row grinding, after grinding terminates, is directly cleaned and is dried, that is, obtain the Heteroatom doping type carbon material；
Wherein described halogenated high-molecular-weight is polyvinylidene fluoride, polyvinylidene chloride or polyvinyl chloride；
Wherein described highly basic is alkali (soil) metal hydroxides, alkali (soil) metal alkoxide, alkali (soil) metal sulfide, alkali
(soil)
Metal amide or alkali (soil) metal nitride；Wherein described " alkali (soil) metal " refers to alkali metal or alkaline earth gold
Category.
Wherein described intensive polar solvent is DMF, DMA, dimethyl sulfoxide (DMSO) or nitrogen
Methyl pyrrolidone；
Wherein described room temperature is 10-40 DEG C.
Wherein described hetero atom refers to the atom of the nonmetalloid outside carbon atom, for example oxygen atom, sulphur atom, nitrogen
Atom, boron atom, phosphorus atoms, etc..
In a preferred embodiment of the invention, before the milling also to adding heteroatom dopant in the mixture, institute
State heteroatom dopant and be selected from melamine, ethylenediamine, thiocarbamide, thioacetamide, boric acid, ammonia borane or triphenylphosphine.
In a preferred embodiment of the invention, the highly basic be NaOH, potassium hydroxide, lithium hydroxide, caustic alcohol,
Vulcanized sodium, Sodamide or lithium nitride.
In a preferred embodiment of the invention, it is described to be ground to hand-ground or ball milling, the duration of the grinding
No less than 1 minute.
Described to be ground to low speed ball milling in more preferred of the invention, so-called low speed ball milling, wherein ball milling is excellent
Elect low speed ball milling as, so-called low speed ball milling refers to the rotating speed not higher than 50Hz of ball mill, it is proposed that using the scope of rotating speed in 10-
40Hz。
In more preferred of the invention, the mole of the highly basic is enough to the halogen in the halogenated high-molecular-weight
Plain atom is substantially completely removed.Substantially completely removing refer to cation in highly basic amount be enough to in the halogenated high-molecular-weight
Whole halogen atoms turn into metal halide normal salt.
In the present invention, heteroatomic doping can be realized by the hetero atom source of three types：One is base of the invention
Intensive polar solvent used in plinth embodiment inherently containing nitrogen-atoms or sulphur atom, can respectively as nitrogen source or
Sulphur source plays a part of to nitrogen or the sulphur of being adulterated in graphitized carbon material.Two is that highly basic of the invention is worked as using vulcanized sodium, Sodamide
Or during lithium nitride, the highly basic can also play the work to adulterated in graphitized carbon material nitrogen or sulphur respectively as nitrogen source or sulphur source in itself
With.Three are, when in preferred embodiments use extra heteroatom dopant, such as melamine, ethylenediamine, thiocarbamide, sulphur
For acetamide, boric acid, ammonia borane or triphenylphosphine, can be played to graphitized carbon as nitrogen source, sulphur source, boron source or phosphorus source respectively
The effect of doping nitrogen, sulphur, boron or phosphorus in material.It is of course also possible to be applied in combination these three doping way or be applied in combination various
Hetero atom source.
Inventor speculate room temperature reaction mechanism of the invention be：Halogen on halogenated high-molecular-weight can be under strong basicity environment
Removing is completed, the halogen of removing can be combined generation metal halide salt with alkali (soil) metallic element contained by above-mentioned highly basic, by force
The protium that the remainder of alkali can face position with halogenated high-molecular-weight halogen is combined generation water.In this way, obtaining high phosphorus content
Carbon material.Because the carbochain after removing functional group has high reactivity, addition that can be selective in the process is adulterated
Agent, in addition highly basic itself and intensive polar solvent can also as dopant, this more prominent this response strategy it is simple and easy to apply.
The method of the present invention compared to other carbon materials room temperature preparation method such as concentrated sulfuric acid evaporation, the reaction controllability compared with
Height, accessory substance is aqueous water and solid base metal halide salt, and any gaseous state waste gas is not produced.Such reaction can be defeated in low energy
Reach reaction completeness higher in the case of entering, and selectable energy input form such as mechanical lapping etc. is simple and easy to apply, it is full
The requirement of full border large-scale production.Carbon source polyvinylidene chloride (10-30 units/kg), polyvinylidene fluoride (80-100 units/kg)
It is cheap, greatly reduce the cost of carbon material end-product.
To sum up, the method for the present invention cost of raw material is cheap, wide material sources, and operation is simple, safe, post processing
It is easy, easily it is applicable industry expanding production.Meanwhile, the strategy also has finger very high for the preparation of new doping carbon material
Lead meaning.Can be carbon based energy source more burning hot at present by being implanted into the concept such as regulation and control and modification in preparation process
Direction provides diversified economy practical carbon material.
Beneficial effect of the present invention is：(1) controllable preparation of room temperature Heteroatom doping carbon material is realized first.(2) from carbon
Arrive the with low cost of the whole flow process of last handling process again to preparation means in source, and pole is applied to industrial expanding production.(3) generate
Accessory substance aqueous water and solid-state metal halide salt are embedded in carbon matrix material, and abundant duct knot can be manufactured after removing
Structure.(4) raw material are technical grade material, extensively, it is cheap, be easy to get, and reflect simple to operate.(5) high-resolution-ration transmission electric-lens photo,
The test display such as carbon nuclear-magnetism spectrum, Raman spectrum, x-ray photoelectron power spectrum, prepared carbon material have carbonizing degree higher and
Relatively low degree of functionality.
Brief description of the drawings
Fig. 1 is the common transmission electron microscope picture of the nitrogen-doped carbon material of preparation in embodiment 1.
Fig. 2 is the high power transmission electron microscope picture of the nitrogen-doped carbon material of preparation in embodiment 1.
Fig. 3 is the scanning electron microscope (SEM) photograph of the nitrogen-doped carbon material of preparation in embodiment 1.
Fig. 4 is the carbon nuclear magnetic spectrogram of the nitrogen-doped carbon material of preparation in embodiment 1.
Fig. 5 is the Raman spectrogram of the nitrogen-doped carbon material of preparation in embodiment 1.
Fig. 6 is the full spectrogram of x-ray photoelectron power spectrum of the nitrogen-doped carbon material of preparation in embodiment 1.
Fig. 7 is the common transmission electron microscope picture of the nitrogen-doped carbon material of preparation in embodiment 2.
Fig. 8 is the scanning electron microscope (SEM) photograph of the nitrogen-doped carbon material of preparation in embodiment 2.
Fig. 9 is the carbon nuclear magnetic spectrogram of the nitrogen-doped carbon material of preparation in embodiment 2.
Figure 10 is the Raman spectrogram of the nitrogen-doped carbon material of preparation in embodiment 2.
Figure 11 is the full spectrogram of x-ray photoelectron power spectrum of the nitrogen-doped carbon material of preparation in embodiment 2.
Figure 12 is the digital apparent spectrogram of the nitrogen-doped carbon material of preparation in embodiment 3.
Figure 13 is the digital apparent spectrogram of the nitrogen-doped carbon material of preparation in embodiment 4.
Figure 14 is the digital apparent spectrogram of the nitrogen-doped carbon material of preparation in embodiment 5.
Figure 15 is the digital apparent spectrogram of the nitrogen-doped carbon material of preparation in embodiment 6.
Specific embodiment
Embodiment 1
1.00 grams of polyvinylidene chloride, 0.60 gram of potassium hydroxide, 10 milliliters of DMFs are added to 30 millis
It is ball grinder is packaged and be provided on ball mill in the zirconia ball grinding jar for rising, carry out ball milling 4 hours, frequency setting is
30.0 hertz.After reaction terminates, add water to stop falling reaction, salt that may be present and is not removed using cleaning centrifugation afterwards
Complete highly basic is reacted, centrifugation product is dried overnight, and sets drying temperature as 60 DEG C.Desciccate is target product.
Specific data：Transmission electron microscope photo is referring to Fig. 1 and Fig. 2.Stereoscan photograph is referring to Fig. 3.Carbon nuclear magnetic spectrogram referring to
Fig. 4.Raman spectrogram is referring to Fig. 5.X-ray photoelectron power spectrum collection of illustrative plates is referring to Fig. 6.
Embodiment 2
1.00 grams of polyvinylidene chloride, 0.60 gram of potassium hydroxide, 10 milliliters of DMFs are added to mortar
In, manual continuously grinding five minutes.Other are with embodiment 1.
Embodiment 3
0.64 gram of polyvinylidene fluoride, 0.60 gram of potassium hydroxide, 10 milliliters of DMFs are added to 30 millis
It is ball grinder is packaged and be provided on ball mill in the zirconia ball grinding jar for rising, carry out ball milling.Other are with embodiment 1.
Embodiment 4
1.00 grams of polyvinylidene chloride, 2.7 gram of nine water vulcanized sodium, 10 milliliters of DMFs are added to 30 millis
It is ball grinder is packaged and be provided on ball mill in the zirconia ball grinding jar for rising, carry out ball milling.Other are with embodiment 1.
Embodiment 5
1.00 grams of polyvinylidene chloride, 0.42 gram of Sodamide, 10 milliliters of DMFs are added to 30 milliliters
Zirconia ball grinding jar in, it is ball grinder is packaged and be provided on ball mill, carry out ball milling.Other are with embodiment 1.
Embodiment 6
1.00 grams of polyvinylidene chloride, 0.38 gram of lithium nitride, 10 milliliters of DMFs are added to 30 milliliters
Zirconia ball grinding jar in, it is ball grinder is packaged and be provided on ball mill, carry out ball milling.Other are with embodiment 1.
Product to obtaining is characterized.The method prepare the typical transmission electron microscope photo of carbon material (Fig. 1 and Fig. 2) and
Stereoscan photograph (Fig. 3) shows that the apparent form of synthesized carbon material is amorphous loose structure, and with to a certain degree
Degree of graphitization, its graphitized area has certain continuity.130-133ppm is located in carbon nuclear magnetic spectrogram (Fig. 4 and Fig. 9)
The corresponding graphitization sp in region peak2The carbon of hydridization, and intensity is higher.The synthesized carbon of Raman collection of illustrative plates (Fig. 5 and Figure 10) display
Material has degree of graphitization higher, there is intensity graphitization G peaks higher.Width in x-ray photoelectron spectroscopy sweeps spectrogram (Fig. 6
And Figure 11) show that having 4 kinds of elements constitutes the Heteroatom doping carbon material, as C, O, N and Cl, corresponding atomic ratio content point
Wei 75.12%, 19.0%, 2.02% and 3.87%.N element derives from highly stable higher boiling intensive polar solvent N, N- bis-
NMF, Cl elements are the Cl on the complete polyvinylidene chloride of unreacted, cause the reason for remaining to be：Poly- inclined two
The granularity of vinyl chloride is larger, about 200-300 microns, and the reaction depth that ball milling method is triggered can not make buried in interior completely
The polyvinylidene chloride reaction in portion is complete.
Claims (7)
1. a kind of room temperature preparation method of Heteroatom doping type carbon material, it is characterised in that it is comprised the following steps：
Halogenated high-molecular-weight, highly basic and intensive polar solvent are mixed to get mixture, the mixture is ground at room temperature then
Mill, after grinding terminates, is directly cleaned and is dried, that is, obtain the Heteroatom doping type carbon material；
Wherein described halogenated high-molecular-weight is polyvinylidene fluoride, polyvinylidene chloride or polyvinyl chloride；
Wherein described highly basic is alkali metal hydroxide, alkali metal alcoholates, alkali metal sulphide, alkali metal amino compound, alkali gold
Category nitride, alkaline earth metal hydroxide, alkaline-earth alkoxides, alkaline earth sulfide, alkaline earth metal amides or alkaline earth
Metal nitride；
Wherein described intensive polar solvent is DMF, DMA, dimethyl sulfoxide (DMSO) or N-methyl
Pyrrolidones；
Wherein described room temperature is 10-40 DEG C.
2. preparation method according to claim 1, it is characterised in that before the milling also to adding miscellaneous original in the mixture
Sub- dopant, the heteroatom dopant is selected from melamine, ethylenediamine, thiocarbamide, thioacetamide, boric acid, ammonia borane or three
Phenylphosphine.
3. preparation method according to claim 1, it is characterised in that the highly basic is NaOH, potassium hydroxide, hydrogen-oxygen
Change lithium, caustic alcohol, vulcanized sodium, Sodamide or lithium nitride.
4. preparation method according to claim 1, it is characterised in that described to be ground to hand-ground or ball milling, it is described to grind
The duration of mill is no less than 1 minute.
5. preparation method according to claim 1, it is characterised in that the mole of the highly basic is enough to the halogenation is high
Halogen atom in molecule is substantially completely removed.
6. preparation method according to claim 2, it is characterised in that the hetero atom refers to non-in addition to carbon atom
The atom of metallic element.
7. preparation method according to claim 2, it is characterised in that the hetero atom is nitrogen, sulphur, boron, phosphorus or oxygen.
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| CN201510316646.5A CN104891475B (en) | 2015-06-10 | 2015-06-10 | A kind of room temperature preparation method of Heteroatom doping type carbon material |
| PCT/CN2015/082609 WO2016197420A1 (en) | 2015-06-10 | 2015-06-29 | Method for preparing doping-type carbon material based on dehalogenation reaction of macromolecule and use of doping-type carbon material in electrochemistry |
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| CN107840318A (en) * | 2016-09-18 | 2018-03-27 | 北京化工大学 | A kind of preparation method with regular pore structure carbon material |
| CN107324310A (en) * | 2017-07-07 | 2017-11-07 | 西安建筑科技大学 | A kind of preparation method of nano-sized carbon |
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