CN108163900A - The preparation method of iron-based oxygen sulphur fluorine or chloride modification three-dimensional graphene composite material - Google Patents
The preparation method of iron-based oxygen sulphur fluorine or chloride modification three-dimensional graphene composite material Download PDFInfo
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- CN108163900A CN108163900A CN201810117518.1A CN201810117518A CN108163900A CN 108163900 A CN108163900 A CN 108163900A CN 201810117518 A CN201810117518 A CN 201810117518A CN 108163900 A CN108163900 A CN 108163900A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide (Fe2O3)
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/12—Sulfides
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
The present invention provides the preparation method of a kind of iron-based oxygen sulphur fluorine or chloride modification three-dimensional graphene composite material.The method includes：Ferric nitrate and polyvinylpyrrolidone dissolving are made into mixed solution by stirring in deionized water；Then the mixed solution of gained is placed in drying box it is dry, pulverize it is last high-temperature process is carried out under protective atmosphere, obtain the composite material of the nano-particle modified three-dimensional porous nitrogen-doped graphene of cementite；Finally the nano-particle modified three-dimensional porous nitrogen-doped graphene composite material of obtained cementite is aoxidized at different temperature respectively, is vulcanized, is fluorinated or chlorination is handled, obtains iron-based oxide, sulfide, fluoride or chloride modification three-dimensional graphene composite material.Procedure according to the present invention is simple, of low cost, with short production cycle, and can prepare on a large scale, and obtained three-dimensional grapheme has higher load area, has broad prospect of application in fields such as energy storage, catalysis.
Description
Technical field
The invention belongs to function nano Material Fields, and in particular to a kind of iron-based oxygen sulphur fluorine or chloride modification three-dimensional graphite
The preparation method of alkene composite material.
Background technology
Graphene as it is a kind of by it is monatomic it is tightly packed into bi-dimensional cellular shape lattice structure carbon material, have many spies
Different physicochemical properties make it show good application prospect in every field.The synthesis of traditional grapheme material
Method has mechanical stripping method, oxidation-reduction method, chemical vapour deposition technique, electrolysis etc., but graphene material prepared by these methods
Expect that yield is smaller, it is of high cost, limit the large-scale application of graphene-based material.The preparation of nano-graphene composite material at present
The emphasis and hot spot of the research of material circle are become with application.Graphene forms multi-element composite material with a variety of basis materials, both may be used
It can expand the use scope of its material again to improve the performance of material.
Iron-based material is due to abundant raw material sources, non-environmental-pollution, safety is good, chemical property is more excellent excellent
Performance obtains the attention of researcher.Iron-based oxide, sulfide, fluoride or the three-dimensional graphene composite material of chloride modification
With superior optics, electricity, magnetic property, have in magnetic material, catalysis material, anti-biotic material, energy and material etc. wide
General application prospect.Therefore research control synthesis iron base oxide, sulfide, fluoride or the three-dimensional grapheme of chloride modification
Composite material, exploitation iron base composite material become one of hot spot direction of investigation of materials.Up to the present, some three-dimensional graphemes
The preparation of material is reported, but is answered about iron-based oxide, sulfide, fluoride or chloride modification three-dimensional grapheme
The synthesis of condensation material is rarely reported.Therefore, control synthesize the iron-based oxide of specific morphology and high-specific surface area, sulfide,
Fluoride or chloride modify the composite material of three-dimensional porous nitrogen-doped graphene, the development for graphene iron base composite material
With extremely important theoretical and practical significance.Through literature survey, iron-based oxide, sulfide, fluoride or chloride are had no
The report of the three-dimensional graphene composite material of modification.
Invention content
The present invention provides the preparation method of a kind of iron-based oxygen sulphur fluorine or chloride modification three-dimensional graphene composite material.
A kind of preparation method of iron-based oxygen sulphur fluorine or chloride modification three-dimensional graphene composite material, it is characterised in that including
Following steps：
1) ferric nitrate and polyvinylpyrrolidone dissolving are made into mixed solution by stirring in deionized water；
2) mixed solution of gained is placed in drying box to dry, the last progress height under protective atmosphere of pulverizing
Temperature processing, obtains the composite material of the nano-particle modified three-dimensional porous nitrogen-doped graphene of cementite；
3) by the composite material of the nano-particle modified three-dimensional porous nitrogen-doped graphene of obtained cementite respectively not
It aoxidized, vulcanized at same temperature, is fluorinated or chlorination is handled, obtained iron-based oxide, sulfide, fluoride or chloride and repair
The three-dimensional graphene composite material of decorations.
Further, the ferric nitrate is nine water ferric nitrates, and polyvinylpyrrolidone is PVP molecular weight K13, K30 and K90
One of which.
Further, the mixed solution ultrasonic agitation time is 10~20min, wherein ferric nitrate and polyvinylpyrrolidine
Ketone mass ratio is (1.0~2.5)：1.
Further, the time of the mixed solution drying is 2~5h, and protective atmosphere is one in nitrogen or argon gas
Kind, temperature is 600~900 DEG C.
Further, the temperature of the composite material oxidation of the nano-particle modified three-dimensional porous nitrogen-doped graphene of the cementite
It is 300~400 DEG C to spend, air atmosphere, and heating rate is 1~10 DEG C/min；Curing temperature is 200~300 DEG C, argon gas or nitrogen
Atmosphere, heating rate are 2~5 DEG C/min；Fluorination or chlorination temperature are 250~350 DEG C, argon gas or nitrogen atmosphere, heating rate
For 1~3 DEG C/min.
Further, the sulphur of the composite material vulcanization of the nano-particle modified three-dimensional porous nitrogen-doped graphene of the cementite
Source is sublimed sulfur, is fluorinated required raw material as ammonium fluoride, and the required raw material of chlorination is ammonium chloride, and wherein iron base composite material is repaiied
The mass ratio of composite material and sublimed sulfur, ammonium fluoride or ammonium chloride for adoring three-dimensional porous nitrogen-doped graphene is 1:(2~6).
The preparation method of a kind of iron-based oxygen sulphur fluorine proposed by the invention or chloride modification three-dimensional graphene composite material,
There is not yet document and other aspects report.Preparation method is simple, and method is novel, with short production cycle, can prepare with scale.And iron-based
Oxide, sulfide, fluoride or the three-dimensional graphene composite material of chloride modification since it is with special three-dimensional structure,
Obtained three-dimensional grapheme has higher load area, has broad prospect of application in fields such as energy storage, catalysis.
This method has the following advantages：
1) method is simple to operation, of low cost, and raw material is easy to get, can be by the way that reaction condition is controlled to adjust the shape of composite material
Looks.
2) high temperature foaming process and second of heat treatment process are combined for the first time, can prepared in a relatively short period of time
The iron-based oxide of different foaming degrees and different-shape, sulfide, fluoride or the three-dimensional grapheme of chloride modification are compound
Material.
3) three-dimensional grapheme prepared by has abundant mesoporous microcellular structure, and large specific surface area can be loaded uniformly
Iron base composite material.
Description of the drawings
Fig. 1 be the ferric oxide nanometer particle for preparing of the present invention modify three-dimensional graphene composite material XRD spectrum (a) and
FESEM photos (b)；
Fig. 2 be the XRD spectrum (a) of the nano-particle modified three-dimensional graphene composite material of iron sulfide prepared by the present invention and
FESEM photos (b)；
Fig. 3 be the XRD spectrum (a) of the nano-particle modified three-dimensional graphene composite material of ferric flouride prepared by the present invention and
FESEM photos (b)；
Fig. 4 be the XRD spectrum (a) of the nano-particle modified three-dimensional graphene composite material of iron chloride prepared by the present invention and
FESEM photos (b)；
Fig. 5 is the AFM photos (a) and line that ferric oxide nanometer particle prepared by the present invention modifies three-dimensional graphene composite material
Sweep curve (b).
Specific embodiment
Embodiment one
Weigh PVP K30 powder and Fe (NO3)3·9H2O mass fractions are 1:1 powder is dissolved in deionization
10min is stirred by ultrasonic in water, the product after mixed solution is completely dried in drying box is ground into powder, and powder is shifted
In N in pipe type sintering furnace22h is kept the temperature under the conditions of 700 DEG C in atmosphere, it is compound to obtain the nano-particle modified three-dimensional grapheme of cementite
Material takes the nano-particle modified three-dimensional graphene composite material of 0.12g cementite in 300 DEG C of conditions of pipe type sintering furnace air atmosphere
Lower heat preservation 1.5h obtains the three-dimensional graphene composite material of ferric oxide nanometer particle modification.
Embodiment two
Weigh PVP K30 powder and Fe (NO3)3·9H2O mass fractions are 1:1.5 powder be dissolved in from
15min is stirred by ultrasonic in sub- water, the product after mixed solution is completely dried in drying box is ground into powder, and powder is turned
It moves in pipe type sintering furnace in N22h is kept the temperature under the conditions of 700 DEG C in atmosphere, the nano-particle modified three-dimensional grapheme of cementite is obtained and answers
Condensation material takes the nano-particle modified three-dimensional graphene composite material of 0.2g cementite to be mixed with 0.4g sublimed sulfurs, is sintered in tubular type
2h is kept the temperature under the conditions of 300 DEG C of stove nitrogen atmosphere, obtains the nano-particle modified three-dimensional graphene composite material of iron sulfide.
Embodiment three
Weigh PVP K30 powder and Fe (NO3)3·9H2O mass fractions are 1:1.2 powder be dissolved in from
20min is stirred by ultrasonic in sub- water, the product after mixed solution is completely dried in drying box is ground into powder, and powder is turned
It moves in pipe type sintering furnace in N22h is kept the temperature under the conditions of 700 DEG C in atmosphere, the nano-particle modified three-dimensional grapheme of cementite is obtained and answers
Condensation material takes the nano-particle modified three-dimensional graphene composite material of 0.21g cementite to be mixed with 0.64g ammonium fluorides, is burnt in tubular type
2h is kept the temperature under the conditions of 270 DEG C of freezing of a furnace nitrogen atmosphere, obtains the nano-particle modified three-dimensional graphene composite material of ferric flouride.
Example IV
Weigh PVP K30 powder and Fe (NO3)3·9H2O mass fractions are 1:1.8 powder be dissolved in from
20min is stirred by ultrasonic in sub- water, the product after mixed solution is completely dried in drying box is ground into powder, and powder is turned
It moves in pipe type sintering furnace in N22h is kept the temperature under the conditions of 700 DEG C in atmosphere, the nano-particle modified three-dimensional grapheme of cementite is obtained and answers
Condensation material takes the nano-particle modified three-dimensional graphene composite material of 0.16g cementite to be mixed with 0.56g ammonium chlorides, is burnt in tubular type
1.5h is kept the temperature under the conditions of 280 DEG C of freezing of a furnace nitrogen atmosphere, obtains the nano-particle modified three-dimensional graphene composite material of iron chloride.
The above embodiments are merely illustrative of the technical scheme of the present invention and are not intended to be limiting thereof, the ordinary skill people of fields
Member, which should be appreciated that, can be modified or replaced equivalently the specific embodiment of the present invention with reference to above-described embodiment, these
Without departing from any modification of spirit and scope of the invention or equivalent replacement apply pending claims it
It is interior.
Claims (6)
1. the preparation method of a kind of iron-based oxygen sulphur fluorine or chloride modification three-dimensional graphene composite material, it is characterised in that including such as
Lower step：
A. ferric nitrate and polyvinylpyrrolidone dissolving are made into mixed solution by ultrasonic agitation in deionized water；
B. the mixed solution of gained is placed in drying box dry, pulverizing last carries out under protective atmosphere at high temperature
Reason, obtains the composite material of the nano-particle modified three-dimensional porous nitrogen-doped graphene of cementite；
C. by the composite material of the nano-particle modified three-dimensional porous nitrogen-doped graphene of obtained cementite respectively different
At a temperature of aoxidized, vulcanize, be fluorinated or chlorination processing, obtain iron-based oxide, sulfide, fluoride or chloride modification
Three-dimensional graphene composite material.
2. the preparation side of iron-based oxygen sulphur fluorine according to claim 1 or the three-dimensional graphene composite material of chloride modification
Method, it is characterised in that ferric nitrate is nine water ferric nitrates in the step a, polyvinylpyrrolidone for PVP molecular weight K13, K30 and
K90 one of which.
3. the preparation side of iron-based oxygen sulphur fluorine according to claim 1 or the three-dimensional graphene composite material of chloride modification
Method, it is characterised in that it is 10~20min, wherein ferric nitrate and polyvinylpyrrolidone matter that the time is stirred by ultrasonic in the step a
Amount is than being (1.0~2.5)：1.
4. the preparation side of iron-based oxygen sulphur fluorine according to claim 1 or the three-dimensional graphene composite material of chloride modification
Method, it is characterised in that the dry time is 2~5h in the step b, and protective atmosphere is one kind in nitrogen or argon gas, temperature
It is 600~900 DEG C.
5. the preparation side of iron-based oxygen sulphur fluorine according to claim 1 or the three-dimensional graphene composite material of chloride modification
Method, it is characterised in that the temperature that composite material aoxidizes in the step c is 300~400 DEG C, air atmosphere, heating rate for 1~
10℃/min；Curing temperature is 200~300 DEG C, and argon gas or nitrogen atmosphere, heating rate are 2~5 DEG C/min；Fluorination or chlorination
Temperature is 250~350 DEG C, and argon gas or nitrogen atmosphere, heating rate are 1~3 DEG C/min.
6. the preparation side of iron-based oxygen sulphur fluorine according to claim 1 or the three-dimensional graphene composite material of chloride modification
Method, it is characterised in that the sulphur source that composite material vulcanizes in the step c is sublimed sulfur, is fluorinated required raw material as ammonium fluoride, chlorine
Change required raw material as ammonium chloride, wherein the composite material of the nano-particle modified three-dimensional porous nitrogen-doped graphene of cementite with
The mass ratio of sublimed sulfur, ammonium fluoride or ammonium chloride is 1:(2~6).
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108929653A (en) * | 2018-06-28 | 2018-12-04 | 北京科技大学 | A kind of three-dimensional grapheme base composite wave-absorbing material and preparation method thereof |
| CN110828819A (en) * | 2019-10-28 | 2020-02-21 | 北京科技大学 | Pyrrhotite type iron sulfide negative electrode material for potassium ion battery and preparation method thereof |
| CN110828796A (en) * | 2019-10-29 | 2020-02-21 | 北京科技大学 | Yolk shell structure potassium ion battery negative electrode material and preparation method thereof |
| CN112234206A (en) * | 2020-10-19 | 2021-01-15 | 中南大学 | Method for preparing thin-layer graphene/transition metal fluoride composite positive active material by using antibiotic fungi residues |
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| CN104134806A (en) * | 2014-07-01 | 2014-11-05 | 南京航空航天大学 | Method for preparing nitrogen-doped graphene/metal complex from bottom to top, product thereof and application of product |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108929653A (en) * | 2018-06-28 | 2018-12-04 | 北京科技大学 | A kind of three-dimensional grapheme base composite wave-absorbing material and preparation method thereof |
| CN110828819A (en) * | 2019-10-28 | 2020-02-21 | 北京科技大学 | Pyrrhotite type iron sulfide negative electrode material for potassium ion battery and preparation method thereof |
| CN110828819B (en) * | 2019-10-28 | 2020-11-27 | 北京科技大学 | Pyrrhotite type iron sulfide negative electrode material for potassium ion battery and preparation method thereof |
| CN110828796A (en) * | 2019-10-29 | 2020-02-21 | 北京科技大学 | Yolk shell structure potassium ion battery negative electrode material and preparation method thereof |
| CN110828796B (en) * | 2019-10-29 | 2020-11-27 | 北京科技大学 | Yolk shell structure potassium ion battery negative electrode material and preparation method thereof |
| CN112234206A (en) * | 2020-10-19 | 2021-01-15 | 中南大学 | Method for preparing thin-layer graphene/transition metal fluoride composite positive active material by using antibiotic fungi residues |
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