CN108360089A - A kind of preparation method and applications of metal oxide porous framework/graphene composite fibre - Google Patents
A kind of preparation method and applications of metal oxide porous framework/graphene composite fibre Download PDFInfo
- Publication number
- CN108360089A CN108360089A CN201810148857.6A CN201810148857A CN108360089A CN 108360089 A CN108360089 A CN 108360089A CN 201810148857 A CN201810148857 A CN 201810148857A CN 108360089 A CN108360089 A CN 108360089A
- Authority
- CN
- China
- Prior art keywords
- graphene
- composite fibre
- metal oxide
- mof
- porous framework
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/10—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material by decomposition of organic substances
Abstract
The invention discloses a kind of preparation method of metal oxide porous framework/graphene composite fibre, the metal oxide porous framework/graphene composite fibre is that graphene oxide (GO) passes through the compound metal oxide porous framework/graphene composite fibre obtained with calcining with MOF crystal powders.Preparation method of the present invention is easy to operate, mild condition, pattern is adjustable, structure-controllable, uniform component distribution, remain the structural intergrity of graphene and the metal oxide porous framework obtained as template using MOF crystal, the excellent properties of graphene and metal oxide porous framework are had both, it being capable of mass or industrialized production, and it is as lithium ion battery negative material, it has excellent performance, there is good application prospect.
Description
Technical field
The present invention relates to composite materials to synthesize field, multiple more particularly, to a kind of metal oxide porous framework/graphene
The preparation method and applications of condensating fiber.
Background technology
With the development of energy storage technology, lithium ion battery has become most popular mobile energy storage device.Lithium-ion electric
Pond has many advantages, such as high-energy-density, long circulation life, high-specific-power, high security, memory-less effect and high output voltage, extensively
Applied in the mobile electronic devices such as computer, mobile phone, electric vehicle.Demand with people to energy storage device constantly increases, existing
Some performance of lithium ion batteries cannot be satisfied the demand of people.
Transition metal oxide is because it generally has high theoretical capacity, for ion cathode material lithium right and wrong often with there is foreground
's.However transition metal oxide negative material there is poorly conductive and in lithium ion battery charge and discharge process metal oxygen
Seriously hinder its application directly as lithium ion battery negative material the shortcomings of compound particle is easily reunited.
Metal-organic framework materials (Metal-organic frameworks, MOF) are that a kind of multidimensional is periodically more
Hole on framework material is mainly coordinated with organic ligand by complexing by transition metal ions.Using MOF as forerunner's system
Standby obtained porous carbon, metal oxide composite etc. is also widely used for clean energy resource storage and conversion system, such as lithium
Battery, fuel cell and ultracapacitor etc..
Graphene possesses the advantages that high theoretical surface, high conductivity, is ideal electrode material.By metal oxide
Compound with graphene, obtained ion cathode material lithium can effective solution metal conductive oxide be poor, charge and discharge process
The problems such as middle metal oxide particle is easily reunited.Porous metal oxide/graphene that gained is prepared by wet spinning process is compound
Fiber can have both the structural advantage of each component, while have the architectural characteristic of fibrous material, in environment, the energy, flexible device
Equal fields have a good application prospect.Therefore, a kind of mild, simple, pervasive method is developed, it is uniform to construct composite distribution,
The metal oxide of pattern and structure-controllable porous framework/graphene composite fibre has a very important significance.
Invention content
The present invention is to overcome the above-mentioned graphene composite material of two and three dimensions in the prior art mechanical strength, electric conductivity
And the problem that flexibility is not high, a kind of metal oxide porous framework based on MOF/graphene composite fibre preparation side is provided
Method, compared to traditional two dimension, three-dimensional graphene composite material, graphene composite fibre has high strength, high conductivity
And the features such as high-flexibility.
To achieve the goals above, the present invention uses following technical scheme：
A kind of preparation method of metal oxide porous framework/graphene composite fibre, the metal oxide porous framework/stone
Black alkene composite fibre is that graphene oxide (GO) passes through the compound porous frame of metal oxide obtained with calcining with MOF crystal powders
Frame/graphene composite fibre.The present invention is almost all suitable for all MOF crystal, and the preparation method of MOF crystal can pass through document
It consults and obtains, such as Fe-MOF, ZIF-8, Co-MOF, Ni-MOF, Cu-MOF crystal can be synthesized by the method for solvent heat；
During being mixed with graphene oxide, a kind of MOF can be added, two or more MOF can also be added.
Preferably, a kind of preparation method of metal oxide porous framework/graphene composite fibre, including following step
Suddenly：Take a concentration of 0.1 ~ 100 mg/mL graphene oxide dispersion and MOF crystal powders in mixing under confined conditions, stir
It is uniform that spinning solution, spinning solution pass through wet spinning, be prepared into a diameter of 20 ~ 50 microns of the compound fibres of graphene oxide/MOF
Dimension, then through 300 ~ 600 DEG C of calcining 0.5-3h, obtain the metal oxide porous framework/graphene composite fibre；Wherein, institute
The mass ratio that feeds intake for stating MOF crystal powders and graphene oxide is (0.1~10)：1.Using technique, wet spinning is simply mixed
And calcining, prepare metal oxide porous framework/compound fibre of graphene of adjustable pattern, structure-controllable, uniform component distribution
Dimension, the preparation method of the composite fibre is easy to operate, mild condition, agents useful for same instrument derive from a wealth of sources, being capable of mass or work
Industry metaplasia is produced；Technical solution of the present invention uses wet spinning process and means of calcination, only by being stirred MOF and graphene
Or two kinds of materials of graphene oxide, it calcines after wet spinning and can be realized；Solvent used in the present invention is in laboratory or industry
It can be obtained in metaplasia production, cheap, derive from a wealth of sources, used experimental facilities is easy to operate, also, in the synthesis process
The integrality for remaining graphene and the metal oxide porous framework structure prepared as template using MOF crystal, is that one kind can
The method for effectivelying prevent graphene film and metal oxide to reunite.
Preferably, the graphene oxide dispersion is graphene oxide water solution or graphene oxide DMF solution,
Preferably graphene oxide DMF solution.
Preferably, graphene surface is aoxidized with metal in the metal oxide porous framework/graphene composite fibre
The complex method of object be graphene coated metal oxide or metal oxide uniform load on the surface of graphene on one kind or
Two kinds, specifically depending on metal oxide nature and addition.
Preferably, the MOF crystal powders are selected from ZIF-8, Ni-MOF, Fe-MOF, MOF-5, Co-MOF or [K2Sn2
(bdc)3](H2O)XOne or more of.Two kinds or more of MOF crystal can be added simultaneously, by being contained after calcining
Metal oxide porous framework/graphene composite fibre of Multimetal oxide.
Preferably, the wet spinning includes the following steps：The spinning solution is continuously injected into injection by syringe
Into coagulating bath, wherein the syringe needle internal diameter of syringe is 0.1-0.5 mm, and outer diameter is 0.12-0.6 mm, length 10-15
Mm, then through vacuum filtration, spontaneously dry, calcining obtains metal oxide porous framework/graphene composite fibre presoma.
Preferably, the mass ratio that feeds intake of the MOF crystal powders and graphene oxide is (1 ~ 2):1；The oxidation stone
Black alkene is sheet, and lateral dimension is 0.1 ~ 100 micron；A concentration of 6 ~ 10 mg/mL of graphene oxide dispersion.
Preferably, the coagulating bath is selected from 5 %wt CaCl2 Aqueous solution, ethyl alcohol, the ethanol solution for being saturated potassium hydroxide
Or any one in ethyl acetate.
Preferably, the coagulating bath is ethyl acetate.
Preferably, the method for calcinating is：First lead to nitrogen so that air is discharged, 500 are warming up to 10 DEG C/min rates ~
600 DEG C, 0.5 ~ 1.5 h is calcined, rear Temperature fall calcines 0.5 ~ 1.5 h to 300 ~ 380 DEG C, and last Temperature fall obtains described
Metal oxide porous framework/graphene composite fibre.
A kind of porous metals that the preparation method of metal oxide porous framework/graphene composite fibre is prepared oxidation
Application of the object/graphene composite fibre in the energy, environment or flexible device field.
It is theoretical based on classical colloid liquid crystal by the property of graphene oxide liquid crystal using technical solution of the present invention, lead to
It crosses and different types of MOF crystal is added, before wet spinning is prepared into one-dimensional metal oxide porous framework/graphene composite fibre
Body is driven, metal oxide porous framework/graphene composite fibre is prepared into after calcining.The graphene film surface of the fiber is uniformly attached
Metal oxide.Prepared metal oxide porous framework/graphene composite fibre has porous structure, the composite fibre
The porous structure being assembled by metal oxide nanoparticles is formed with redox graphene, in the synthesis process, is remained
The structural intergrity of graphene and the metal oxide porous framework obtained as template using MOF crystal, has both graphene and metal
The excellent properties of oxide porous frame can play graphene and more simultaneously in the fields such as sensing, catalysis, energy storage, absorption
The excellent properties of both mesoporous metal oxides, and metal oxide porous framework/graphene composite fibre has certain flexibility,
There is bright application prospect in flexible electronic device.
Therefore, the present invention has the advantages that：（1）Preparation method is easy to operate, mild condition, pattern is adjustable, knot
Structure is controllable, uniform component distribution；（2）It being capable of mass or industrialized production；（3）Preparation method remains graphene and with MOF
Crystal is the structural intergrity for the metal oxide porous framework that template obtains, and has had both graphene and the porous frame of metal oxide
The excellent properties of frame.
Description of the drawings
Fig. 1: Fe-MOF（a,b）Crystal scanning electron microscope (SEM) photograph.
Fig. 2: Co-MOF（a,b）Crystal scanning electron microscope (SEM) photograph.
Fig. 3:Porous C o3O4The transmission electron microscope picture (a) of/graphene composite fibre presoma;Porous C o3O4/ graphene is multiple
The transmission electron microscope picture (b) of condensating fiber.
Fig. 4：Porous C o3O4The transmission electron microscope Elemental redistribution spectrogram of/graphene composite fibre.
Fig. 5:Porous C o3O4The scanning electron microscope (SEM) photograph of/graphene composite fibre: Fe2O3:rGO=3:2 (a,b)。
Fig. 6:Porous Fe2O3The scanning electron microscope (SEM) photograph of/graphene composite fibre: Co3O4:rGO=3:2 (a,b)。
Fig. 7:Porous Fe2O3/Co3O4The scanning electron microscope (SEM) photograph of/graphene composite fibre：Fe-MOF：Co3O4:GO=3:3:4
(a,b)
Fig. 8：Porous C o3O4The scanning electron microscope Elemental redistribution spectrogram of/graphene composite fibre.
Fig. 9：Porous Fe2O3The scanning electron microscope Elemental redistribution spectrogram of/graphene composite fibre.
Figure 10：Porous Fe2O3/ Co3O4The scanning electron microscope Elemental redistribution spectrogram of/graphene composite fibre.
Figure 11:Porous Fe2O3The XRD spectra (a) of/graphene composite fibre;Porous C o2O3/ graphene composite fibre
XRD spectra (b).
Figure 12:(a) porous Fe2O3(electric current is close for the lithium ion battery charging and discharging curve of/graphene composite fibre negative material
Degree: 100 mA/g;Voltage range: 0.01-3.00 V) ；(b) porous Fe2O3The lithium of/graphene composite fibre negative material from
Sub- battery charging and discharging cyclic curve (current density: 500 mA/g;Voltage range: 0.01-3.00 V)；(c) porous Fe2O3/
The lithium ion battery high rate performance curve (voltage range of graphene composite fibre negative material: 0.01-3.00 V）
Figure 13：(a) porous C o3O4Lithium ion battery charging and discharging curve (the current density of/graphene composite fibre negative material:
100 mA/g；Voltage range: 0.01-3.00 V) ；(b) porous C o3O4The lithium-ion electric of/graphene composite fibre negative material
Pond charge and discharge cycles curve (current density: 946 mA/g;Voltage range: 0.01-3.00 V);(c) porous C o3O4/ graphite
The lithium ion battery high rate performance curve (voltage range of alkene composite fibre negative material: 0.01-3.00 V）.
Figure 14：(a) porous C o3O4/ Fe2O3The lithium ion battery charging and discharging curve of/graphene composite fibre negative material
(current density: 100 mA/g；Voltage range: 0.01-3.00 V) ；(b) porous C o3O4/ Fe2O3/ graphene composite fibre
The lithium ion battery charge and discharge cycles curve (current density of negative material: 1000 mA/g;Voltage range: 0.01-3.00
V);(c) porous C o3O4/ Fe2O3The lithium ion battery high rate performance curve (voltage zone of/graphene composite fibre negative material
Between: 0.01-3.00 V）.
Specific implementation mode：
With reference to specific embodiments and the drawings, the present invention is described in further detail, but embodiments of the present invention are not
It is only limitted to this.Agents useful for same of the present invention is routine experiment or acquisition purchased in market.
Embodiment 1：
A kind of preparation method of metal oxide porous framework/graphene composite fibre, includes the following steps：
（1）The preparation of Fe-MOF crystal powders：At room temperature, the N of 50 mL, N- dimethyl methyls are added in the reaction bulb of 100 mL
The anhydrous ferric chloride of 0.83 g terephthalic acid (TPA)s and 1.215 g is added in amide under magnetic stirring, after it is completely dissolved,
12 h are reacted under 100 DEG C of oil bath.After reaction, through low-speed centrifugal（15 min, room temperature, 4000 rpm）, remove supernatant
Liquid, with ethyl alcohol repeated washing, centrifugation 3 times.Products therefrom finally obtains Fe-MOF crystal powders after 60 DEG C are dried in vacuo 24 h
End；
（2）The preparation of metal oxide porous framework/graphene composite fibre：Oxygen is sequentially added in the centrifuge tube of 5 mL sizes
Graphite alkene DMF solution, Fe-MOF crystal powders, the initial rate of charge for controlling each raw material are as follows：Graphene oxide solution, concentration
6.7 mg/mL, graphene oxide sheet lateral dimension are 50 μm；30 mg of Fe-MOF crystal powders, graphene oxide and Fe-MOF
The dispensing mass ratio of crystal powder is 2：3；Gained mixture is obtained in persistently mixing 2 min through magnetic agitation under confined conditions
GO/Fe-MOF plural gels, i.e. spinning solution, spinning solution is further through wet spinning, specially：Spinning solution is continuous by syringe
It is injected into ethyl acetate coagulating bath, then through vacuum filtration, spontaneously dries, obtain fibrous presoma；It again will be before threadiness
It drives body to be calcined, specially：First lead to nitrogen, is warming up to 450 degrees Celsius with 10 degree of rates per minute, calcines one hour, after
Temperature fall is calcined one hour to 380 degrees Celsius in air, last Temperature fall, obtains a diameter of 25 microns of metal
Oxide porous frame/graphene composite fibre.
It chooses sample in embodiment to be characterized and analyzed, test result is as follows:
Fig. 1（a, b）It is the SEM figures of the Fe-MOF crystal powders obtained in embodiment 1, the Fe- obtained is can be seen that from Fig. 1 b
MOF crystal is polygon spindle, and lateral dimension is hundreds of nanometers.Fig. 6（a, b）It is the metal oxygen obtained in embodiment 1
The surface topography of compound porous framework/graphene composite fibre, Fig. 6 a illustrate the whole pattern of fiber, it can be seen that one-dimensional knot
Structure is to be formed by a large amount of rGO oblique cut graftings, and uniformly adhere to porous Fe above2O3, fiber thickness is 30 microns；Fig. 6 b are figures
6a partial enlarged views, from（b）This it appears that rGO pieces are transparent, illustrate that rGO pieces are not reunited, further proves
The porous structure of this self-supporting is constructed by a large amount of single layer rGO pieces；Porous Fe2O3RGO pieces surface is all spread
It is full, and without finding porous Fe2O3Agglomeration intuitively demonstrates porous Fe2O3With rGO pieces by uniform compound, and at
Work(obtains one dimension fibre structure.Fig. 9 SEM Elemental redistribution spectrograms show C element, O elements, Fe elements in the sample uniform
Distribution, further secondary proof porous Fe2O3In being uniformly distributed for rGO on pieces.Figure 11 (a) gives made in embodiment 1
The XRD spectra of sample, XRD spectra demonstrate the metal in example 1 and aoxidize porous framework/graphene composite fibre by Fe2O3And
RGO is formed.
The porous metal oxide/graphene composite fibre has height as the lithium ion battery that negative material is prepared
Specific capacity, high rate performance and good cyclical stability.Figure 12 shows its chemical property figure, is 100 in current density
MA/g, voltage range:Under the test condition of 0.01-3.00 V, first circle charging and discharging capacity is respectively up to 970.6 and 1477.9
MAh/g, coulombic efficiency is up to 65.67 % for the first time.And it has outstanding performance in terms of stability, high rate performance.
Embodiment 2：
A kind of preparation method of metal oxide porous framework/graphene composite fibre, includes the following steps：
（1）The preparation of Co-MOF crystal powders：Take one 50 mL beakers that the mixed solution of 20 mL methanol and 20 mL ethyl alcohol is added,
The cabaltous nitrate hexahydrate of 725 mg is dissolved in mixed liquor, stirring is until be completely dissolved.It is added 20 in the beaker of another 50 mL
The 2-methylimidazole of 821 mg is dissolved in the mixed liquor by the mixed solution of mL methanol and 20 mL ethyl alcohol, and stirring is until completely molten
Solution.Solution in above-mentioned two beaker is mixed evenly, reacts 24 h at room temperature.After reaction, it centrifuges（15 min, room
Temperature, 4000 rpm）, remove supernatant, after wash 3 times with methanol, products therefrom through 60 DEG C vacuum drying 24 h after, finally obtain
Obtain Co-MOF crystal powders；
（2）Graphene oxide DMF solution, Co-MOF crystal powders are sequentially added in the centrifuge tube of 5 mL sizes, control each original
The initial rate of charge of material is as follows：Graphene oxide solution, 6 mg/mL of concentration, graphene oxide sheet lateral dimension are 75 microns；
The dispensing mass ratio of 30 mg of Co-MOF crystal powders, graphene oxide and Co-MOF crystal powders is 1：1；Gained mixture in
2 min are persistently mixed through magnetic agitation under confined conditions, obtain GO/Co-MOF plural gels, is i.e. spinning solution, spinning solution is further
Through wet spinning, specially：Spinning solution is continuously injected into ethyl acetate coagulating bath by syringe, then is taken out through vacuum
Filter spontaneously dries, obtains a diameter of 30 microns of graphene oxides/MOF composite fibres；Again by graphene oxide/MOF composite fibres into
Row calcining, specially：First lead to nitrogen, is warming up to 480 degrees Celsius with 10 degrees centigrade rates per minute, calcines one hour, afterwards certainly
It so cools to 380 degrees Celsius to calcine one hour in air, last Temperature fall, obtains a diameter of 35 microns of metal oxidation
Object porous framework/graphene composite fibre.
It chooses sample in embodiment to be characterized and analyzed, test result is as follows:Fig. 2（A, b）It is to be obtained in embodiment 2
Co-MOF crystal powders SEM figures, it is gengon that the Co-MOF crystal obtained is can be seen that from Fig. 2 b, and lateral dimension is several
Hundred nanometers.Fig. 5（A, b）It is the surface shape of metal oxide porous framework/graphene composite fibre obtained in embodiment 1
Looks, Fig. 5 a illustrate the whole pattern of fiber, it can be seen that one-dimentional structure be formed by a large amount of rGO oblique cut graftings, and above
It is even to adhere to porous C o3O4, fiber thickness is 35 microns；Fig. 5 b are Fig. 5 a partial enlarged views, from b this it appears that rGO pieces are
Transparent, illustrate that rGO pieces are not reunited, further proves that the porous structure of this self-supporting is by a large amount of single layer rGO pieces
It constructs；Porous C o3O4RGO pieces surface is all paved with, and without finding porous C o3O4Agglomeration, intuitively
Demonstrate porous C o3O4With rGO pieces by uniform compound, and successfully obtain one dimension fibre structure.Fig. 8 SEM Elemental redistribution spectrograms
Show C element, O elements, Co elements being uniformly distributed in the sample, further secondary proof porous C o3O4In rGO on pieces
Be uniformly distributed.Fig. 3 is the TEM figures of example 2, and Co-MOF crystal and GO are uniformly compound it can be seen from Fig. 3 a, can be with by Fig. 3 b
Find out, which is by Co3O4The porous structure that nano particle is assembled into is formed with redox graphene.Fig. 4 TEM members
Plain distribution profile figure has shown C element, O elements, Co elements being uniformly distributed in the sample, and it is Co to further demonstrate the structure3O4
The porous structure that nano particle is assembled into.Figure 11 (b) gives the XRD spectra of made sample in embodiment 2, and XRD spectra proves
Metal in example 2 aoxidizes porous framework/graphene composite fibre by Co3O4And rGO compositions.
The lithium ion battery tool that the metal oxide porous framework/graphene composite fibre is prepared as negative material
There are height ratio capacity, high rate performance and good cyclical stability.Figure 13 shows its chemical property figure, is in current density
100 mA/g, voltage range:Under the test condition of 0.01-3.00 V, first circle charging and discharging capacity is respectively up to 916.8 Hes
1312.5 mAh/g, coulombic efficiency is up to 69.85% for the first time.And it has outstanding performance in terms of stability, high rate performance.
Embodiment 3：
A kind of preparation method of metal oxide porous framework/graphene composite fibre, includes the following steps：In 5mL sizes
Graphene oxide DMF solution, Fe-MOF crystal powders, Co-MOF crystal powders are sequentially added in centrifuge tube, control each raw material
Initial rate of charge is as follows：Graphene oxide solution, 6.7 mg/mL of concentration, graphene oxide sheet lateral dimension are 50 microns；Fe-
MOF crystal powders 15 mg, Co-MOF crystal powder 15mg, graphene oxide, Fe-MOF crystal powders and Co-MOF crystal powders
Dispensing mass ratio be 4:3:3；Gained mixture obtains compound solidifying in persistently mixing 2min through magnetic agitation under confined conditions
Glue, i.e. spinning solution, spinning solution is further through wet spinning, specially：Spinning solution is continuously injected into acetic acid by syringe
In ethyl ester coagulating bath, then through vacuum filtration, spontaneously dries, obtain a diameter of 25 microns of graphene oxides/MOF composite fibres；Again will
Graphene oxide/MOF composite fibres are calcined, specially：First lead to nitrogen, it is Celsius to be warming up to 450 with 10 degree of rates per minute
Degree is calcined one hour, and rear Temperature fall is calcined one hour to 380 degrees Celsius in air, and last Temperature fall obtains the diameter
For 35 microns of metal oxide porous framework/graphene composite fibre.
It chooses sample in embodiment to be characterized and analyzed, test result is as follows：
Surface topography such as Fig. 7 of metal oxide porous framework/graphene composite fibre obtained in embodiment 3（A, b）.Figure
7（a）Illustrate the whole pattern of fiber, it can be seen that one-dimentional structure be formed by a large amount of rGO oblique cut graftings, and above uniformly it is attached
Porous C o3O4/Fe2O3, fiber thickness is 35 microns；Fig. 7（b）It is Fig. 7（a）Partial enlarged view, from（b）It can obviously see
It is transparent to go out rGO pieces, illustrates that rGO pieces are not reunited, and further proves that the porous structure of this self-supporting is by a large amount of
Single layer rGO pieces are constructed；Porous C o3O4/Fe2O3RGO pieces surface is all paved with, and without finding porous C o3O4
And Fe2O3Agglomeration intuitively demonstrates porous C o3O4/ Fe2O3With rGO pieces by uniform compound, and successfully obtain one-dimensional
Fibre structure.Figure 10 SEM Elemental redistribution spectrograms show uniform point of C element, O elements, Co elements, Fe elements in the sample
Cloth, further secondary proof porous C o3O4/ Fe2O3In being uniformly distributed for rGO on pieces.
The lithium ion battery tool that the metal oxide porous framework/graphene composite fibre is prepared as negative material
There are height ratio capacity, high rate performance and good cyclical stability.Figure 14 shows its chemical property figure, in current density
For 100 mA/g, voltage range:Under the test condition of 0.01-3.00 V, first circle charging and discharging capacity is respectively up to 933.3 Hes
1306.4 mAh/g, coulombic efficiency is up to 71.44 % for the first time.And it has outstanding performance in terms of stability, high rate performance.
Embodiment 4：
A kind of preparation method of metal oxide porous framework/graphene composite fibre, includes the following steps：
（1）The preparation method is the same as that of Example 1 for Fe-MOF crystal powders；
（2）Graphene oxide DMF solution, Fe-MOF crystal powders are then sequentially added in the centrifuge tube of 5 mL sizes, are controlled
The initial rate of charge of each raw material is as follows：Graphene oxide solution, 100 mg/mL of concentration, graphene oxide sheet lateral dimension are 100
Micron；The dispensing mass ratio of 20 mg of Fe-MOF crystal powders, graphene oxide and Fe-MOF crystal powders is 1：10；Gained is mixed
Object is closed in persistently mixing 5 min through magnetic agitation under confined conditions, obtains GO/Fe-MOF plural gels, i.e. spinning solution, spinning solution
Further through wet spinning, specially：Spinning solution is continuously injected into ethyl acetate coagulating bath by syringe, then through true
Sky filters, and spontaneously dries, obtains a diameter of 50 microns of graphene oxides/MOF composite fibres；Again by the compound fibres of graphene oxide/MOF
Dimension is calcined, specially：First lead to nitrogen, is warming up to 450 degrees Celsius with 10 degree of rates per minute, calcines 0.5 hour, it is rear natural
It cools to 350 degrees Celsius to calcine 0.5 hour in air, last Temperature fall obtains the metal oxide porous framework/graphite
Alkene composite fibre.
Embodiment 5：
A kind of preparation method of metal oxide porous framework/graphene composite fibre, includes the following steps：
（1）The preparation method is the same as that of Example 1 for Fe-MOF crystal powders；
（2）Graphene oxide DMF solution, Fe-MOF crystal powders are sequentially added in the centrifuge tube of 5 mL sizes, control each original
The initial rate of charge of material is as follows：Graphene oxide solution, 10 mg/mL of concentration, graphene oxide sheet lateral dimension are 50 microns；
The dispensing mass ratio of 40 mg of Fe-MOF crystal powders, graphene oxide and Fe-MOF crystal powders is 1：2；Gained mixture in
5 min are persistently mixed through magnetic agitation under confined conditions, obtain GO/Fe-MOF plural gels, is i.e. spinning solution, spinning solution is further
Through wet spinning, specially：Spinning solution is continuously injected into ethyl acetate coagulating bath by syringe, then is taken out through vacuum
Filter spontaneously dries, obtains a diameter of 30 microns of graphene oxides/MOF composite fibres；Again by graphene oxide/MOF composite fibres into
Row calcining, specially：First lead to nitrogen, is warming up to 450 degrees Celsius with 10 centigrade per minute rates, calcines 1 hour, drop naturally afterwards
Temperature is calcined 2 hours to 300 degrees Celsius in air, last Temperature fall, and it is multiple to obtain the metal oxide porous framework/graphene
Condensating fiber.
In conclusion can successfully prepare the metal that each component is evenly distributed, appearance structure is controllable by our method
Oxide porous frame/graphene composite fibre, the porous structure which is assembled by metal oxide nanoparticles
It is formed with redox graphene, and the composite fibre is had excellent performance as lithium ion battery negative material, has and answer well
Use foreground.
Claims (10)
1. a kind of preparation method of metal oxide porous framework/graphene composite fibre, which is characterized in that the metal oxidation
Object porous framework/graphene composite fibre is that graphene oxide (GO) passes through the compound gold obtained with calcining with MOF crystal powders
Belong to oxide porous frame/graphene composite fibre.
2. a kind of preparation method of metal oxide porous framework/graphene composite fibre according to claim 1, special
Sign is, take a concentration of 0.1 ~ 100 mg/mL graphene oxide dispersion and MOF crystal powders in mixing under confined conditions,
Spinning solution is stirred evenly to obtain, spinning solution passes through wet spinning, it is compound to be prepared into a diameter of 20 ~ 50 microns of graphene oxide/MOF
Fiber, then through 300 ~ 600 DEG C of calcining 0.5-3h, obtain metal oxide porous framework/graphene composite fibre；Wherein, described
The mass ratio that feeds intake of MOF crystal powders and graphene oxide is（0.1~10）：1.
3. a kind of preparation method of metal oxide porous framework/graphene composite fibre according to claim 2, special
Sign is that the graphene oxide dispersion is graphene oxide water solution or graphene oxide DMF solution.
4. a kind of preparation method of metal oxide porous framework/graphene composite fibre according to claim 2, special
Sign is that surface of graphene oxide and the complex method of MOF crystal powders are oxidation stone in the graphene/MOF composite fibres
The one or two of black alkene cladding MOF crystal powders or MOF crystal powder uniform loads in surface of graphene oxide.
5. a kind of preparation method of metal oxide porous framework/graphene composite fibre according to claim 2 or 4,
It is characterized in that, the MOF crystal powders are selected from ZIF-8, Ni-MOF, Fe-MOF, MOF-5, Co-MOF or [K2Sn2(bdc)3]
(H2O)XOne or more of.
6. a kind of preparation method of metal oxide porous framework/graphene composite fibre according to claim 5, special
Sign is that the wet spinning includes the following steps：The spinning solution is continuously injected into coagulating bath by syringe,
Again through vacuum filtration, spontaneously dries, obtain the graphene oxide/MOF composite fibres.
7. a kind of metal oxide porous framework/graphene composite fibre according to claim 2,3 or 6 any one
Preparation method, which is characterized in that the mass ratio that feeds intake of the MOF crystal powders and graphene oxide is (1 ~ 2):1；The oxidation
Graphene is sheet, and lateral dimension is 0.1 ~ 100 micron；A concentration of 6 ~ 10 mg/mL of graphene oxide dispersion.
8. a kind of preparation method of metal oxide porous framework/graphene composite fibre according to claim 6, special
Sign is that the coagulating bath is selected from CaCl2Aqueous solution, ethyl alcohol are saturated in the ethanol solution or ethyl acetate of potassium hydroxide arbitrarily
It is a kind of；Wherein, the CaCl2CaCl in aqueous solution2Mass fraction be 5%.
9. a kind of preparation method of metal oxide porous framework/graphene composite fibre according to claim 8, special
Sign is that the method for calcinating is：First lead to nitrogen so that air is discharged, is warming up to 500 ~ 600 DEG C with 10 DEG C/min rates, calcining
0.5 ~ 1.5h, rear Temperature fall calcine 0.5 ~ 1.5h to 300 ~ 380 DEG C, and it is more to obtain the metal oxide for last Temperature fall
Hole frame/graphene composite fibre.
10. a kind of metal oxide porous framework/graphene composite fibre according to claim 1,3 or 9 any one
Graphene/metal organic frame composite fibre answering in the energy, environment or flexible device field for being prepared of preparation method
With.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810148857.6A CN108360089A (en) | 2018-02-13 | 2018-02-13 | A kind of preparation method and applications of metal oxide porous framework/graphene composite fibre |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810148857.6A CN108360089A (en) | 2018-02-13 | 2018-02-13 | A kind of preparation method and applications of metal oxide porous framework/graphene composite fibre |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108360089A true CN108360089A (en) | 2018-08-03 |
Family
ID=63002612
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810148857.6A Withdrawn CN108360089A (en) | 2018-02-13 | 2018-02-13 | A kind of preparation method and applications of metal oxide porous framework/graphene composite fibre |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108360089A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109659111A (en) * | 2019-02-01 | 2019-04-19 | 杭州高烯科技有限公司 | A kind of graphene-ferrimagnetism composite membrane and preparation method thereof |
| CN109713266A (en) * | 2018-12-24 | 2019-05-03 | 肇庆市华师大光电产业研究院 | A kind of novel cathode material for lithium ion battery and preparation method thereof |
| CN109860558A (en) * | 2019-02-01 | 2019-06-07 | 杭州高烯科技有限公司 | A kind of lithium ion battery graphene-iron oxide film and the preparation method and application thereof |
| CN109972224A (en) * | 2019-04-10 | 2019-07-05 | 上海科碳新材料科技有限公司 | A kind of ultra-high molecular weight polyethylene base graphene receives micro- self assembly fiber and preparation method thereof |
| CN110396731A (en) * | 2019-04-25 | 2019-11-01 | 北京航空航天大学 | A kind of preparation method of bionical high-strength and high ductility nano-composite fiber |
| CN111188196A (en) * | 2020-01-19 | 2020-05-22 | 北京化工大学 | Preparation and application of graphene composite fiber non-woven fabric for catalytic degradation of neurogenic chemical warfare agent |
| CN112726193A (en) * | 2020-12-21 | 2021-04-30 | 华中科技大学 | Cobalt-nitrogen co-doped carbon nanotube modified graphene fiber, and preparation and application thereof |
| CN112798665A (en) * | 2021-01-08 | 2021-05-14 | 江西农业大学 | Preparation method and application of copper-based-organic metal framework electrochemical sensor for measuring zearalenone |
-
2018
- 2018-02-13 CN CN201810148857.6A patent/CN108360089A/en not_active Withdrawn
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109713266A (en) * | 2018-12-24 | 2019-05-03 | 肇庆市华师大光电产业研究院 | A kind of novel cathode material for lithium ion battery and preparation method thereof |
| CN109659111A (en) * | 2019-02-01 | 2019-04-19 | 杭州高烯科技有限公司 | A kind of graphene-ferrimagnetism composite membrane and preparation method thereof |
| CN109860558A (en) * | 2019-02-01 | 2019-06-07 | 杭州高烯科技有限公司 | A kind of lithium ion battery graphene-iron oxide film and the preparation method and application thereof |
| CN109659111B (en) * | 2019-02-01 | 2020-12-08 | 杭州高烯科技有限公司 | Graphene-ferrite magnetic composite film and preparation method thereof |
| CN109972224A (en) * | 2019-04-10 | 2019-07-05 | 上海科碳新材料科技有限公司 | A kind of ultra-high molecular weight polyethylene base graphene receives micro- self assembly fiber and preparation method thereof |
| CN110396731A (en) * | 2019-04-25 | 2019-11-01 | 北京航空航天大学 | A kind of preparation method of bionical high-strength and high ductility nano-composite fiber |
| CN111188196A (en) * | 2020-01-19 | 2020-05-22 | 北京化工大学 | Preparation and application of graphene composite fiber non-woven fabric for catalytic degradation of neurogenic chemical warfare agent |
| CN112726193A (en) * | 2020-12-21 | 2021-04-30 | 华中科技大学 | Cobalt-nitrogen co-doped carbon nanotube modified graphene fiber, and preparation and application thereof |
| CN112726193B (en) * | 2020-12-21 | 2022-03-18 | 华中科技大学 | Cobalt-nitrogen co-doped carbon nanotube modified graphene fiber, and preparation and application thereof |
| CN112798665A (en) * | 2021-01-08 | 2021-05-14 | 江西农业大学 | Preparation method and application of copper-based-organic metal framework electrochemical sensor for measuring zearalenone |
| CN112798665B (en) * | 2021-01-08 | 2023-02-17 | 江西农业大学 | Preparation method and application of copper-based-organic metal framework electrochemical sensor for measuring zearalenone |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108360089A (en) | A kind of preparation method and applications of metal oxide porous framework/graphene composite fibre | |
| CN108360090A (en) | A kind of preparation method and applications of metal selenide porous framework/graphene composite fibre | |
| Zhao et al. | Facile synthesis of nanoporous γ-MnO2 structures and their application in rechargeable Li-ion batteries | |
| CN108456936A (en) | A kind of preparation method and applications of metal sulfide porous framework/graphene composite fibre | |
| CN108441982A (en) | A kind of preparation method of graphene/metal organic frame composite fibre | |
| CN106450205A (en) | Two-dimensional transition metal carbide (nitride) and nano sulfur particulate composite as well as preparation and application thereof | |
| CN111362254A (en) | Preparation method and application of nitrogen-doped carbon nanotube-loaded phosphorus-doped cobaltosic oxide composite material | |
| JP5270503B2 (en) | Method for producing transition metal oxide rod, method for producing secondary battery | |
| CN110079895B (en) | Titanate and titanium dioxide composite nanowire and preparation method thereof | |
| CN108360091A (en) | A kind of preparation method and applications of metal phosphide porous framework/graphene composite fibre | |
| CN113571674B (en) | Preparation method and application of in-situ carbon-coated binary transition metal oxide heterojunction bowl-shaped nano composite material | |
| CN108190963A (en) | A kind of hollow CoFe of multistage2O4Material, CoFe2O4The preparation method and application of/C composite | |
| CN111099650A (en) | CeO2Molten salt method for synthesizing nano spherical particles | |
| CN1817800A (en) | Synthesis of series nanometer lithium and manganese oxide for lithium ion battery | |
| CN109336196A (en) | Three-dimensional fine and close macroscopic body of metal sulfide porous framework/graphene and preparation method thereof, application | |
| CN110707301A (en) | Vanadium trioxide/carbon composite material with nanosphere structure and preparation method and application thereof | |
| CN113410443A (en) | Preparation method and application of high-stability copper intercalation manganese dioxide electrode material | |
| CN111564323B (en) | Cobalt pyrovanadate nano material and preparation method and application thereof | |
| CN104103822B (en) | Preparation method of lithium ion battery cathode material | |
| CN111924864A (en) | MnO/MgO composite negative electrode material of lithium ion battery and preparation method thereof | |
| CN113571681B (en) | Hollow titanium dioxide/nickel/carbon composite material and preparation method and application thereof | |
| Hua et al. | Green synthesis and electrochemical properties of A3 (PO4) 2 (A= Mn, Zn, and Co) hydrates for supercapacitors with long-term cycling stability | |
| CN1312330C (en) | α－MnO 2 Preparation method of single crystal nanorod | |
| CN109256536A (en) | Lithium titanate flexible self-supporting combination electrode and preparation method thereof | |
| CN109904436B (en) | Cobalt titanate titanium dioxide composite nanowire and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20180803 |