CN108360090A - A kind of preparation method and applications of metal selenide porous framework/graphene composite fibre - Google Patents
A kind of preparation method and applications of metal selenide porous framework/graphene composite fibre Download PDFInfo
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- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
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Abstract
The invention discloses a kind of preparation methods of metal selenide porous framework/graphene composite fibre, metal selenide porous framework/graphene the composite fibre using MOF crystal powders and graphene oxide by compound obtained fibrous composite as presoma, obtained by calcining.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 selenide porous framework obtained as template using MOF crystal, the excellent properties of graphene and metal selenide 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 selenide 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.
The electrochemical reaction process of transition metal selenides is generally polyelectron reaction, and it is with higher capacity.But
It is in electrochemical reaction process, electrode material volume change is serious, easily causes electrode dusting, to reduce its working efficiency
With the service life.And more selenides that deep discharge generates are soluble in electrolyte, cause the loss of active material.According to the literature, greatly
Mostly use carbon material modification, such as inhibit the expansion of electrode material with the mode of load or carbon coated, reduce more selenides and
The contact of electrolyte, to effectively improve the cyclical stability and high rate performance of material.
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 selenide composite material 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 selenide
Compound with graphene, obtained ion cathode material lithium being capable of effective solution metal selenide poorly conductive, charge and discharge process
The problems such as middle metal selenide particle is easily reunited.Porous metals selenides/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 selenide 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, provide a kind of metal sulfide porous framework/graphene composite fibre preparation method and its
Using compared to traditional two dimension, three-dimensional graphene composite material, metal selenide porous framework/graphene composite fibre tool
There is the features such as high strength, high conductivity and high-flexibility.
To achieve the goals above, the present invention uses following technical scheme:
A kind of metal selenide porous framework/graphene composite fibre, the metal selenide porous framework/compound fibre of graphene
It ties up using MOF crystal powders and graphene oxide through compound obtained fibrous composite as presoma, is obtained by calcining.
A kind of preparation method of metal selenide porous framework/graphene composite fibre, includes the following steps:
(1)Take the graphene oxide dispersion of MOF crystal powders and a concentration of 0.1 ~ 100 mg/mL in mixing under confined conditions,
Stir evenly to obtain spinning solution;Wherein, the mass ratio that feeds intake of the MOF crystal powders and graphene oxide is (0.1~10):1;
(2)Above-mentioned spinning solution is obtained into metal selenide porous framework/graphene composite fibre presoma by wet spinning;
(3)By step(2)Described in selenium powder is added in presoma, through 300 ~ 600 DEG C of 1 ~ 20 h of calcining, be prepared into a diameter of 20 ~
50 microns of composite fibre, i.e., described metal selenide porous framework/graphene composite fibre.Using technique, wet is simply mixed
Method spinning and calcining prepare metal selenide porous framework/graphene of adjustable pattern, structure-controllable, uniform component distribution
Composite fibre, 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 batch
Change or industrialized production;Technical solution of the present invention use wet spinning process and means of calcination, only by be stirred MOF with
Two kinds of materials of graphene or graphene oxide are calcined after wet spinning and be can be realized;Solvent used in the present invention is in laboratory
Or can be obtained in industrialized production, cheap, derive from a wealth of sources, used experimental facilities is easy to operate, also, is synthesizing
The integrality for remaining graphene and the metal selenide porous framework structure prepared as template using MOF crystal in the process, is one
The method that graphene film and metal selenide kind can be effectively prevent to reunite, prepare the metal selenide porous framework of gained/
Graphene composite fibre shows the excellent electrochemical properties such as high power capacity, high stability as the negative material of lithium ion, described
Metal selenide porous framework/graphene composite fibre length is adjustable, it is the compound fibre within the scope of 0.5 ~ 50 cm that can prepare length
Dimension,
Preferably, the graphene oxide dispersion is graphene oxide/aqueous solution or graphene oxide/N, N- dimethyl methyls
Amide (DMF) solution, preferably graphene oxide DMF solution.
Preferably, graphene surface and metal selenizing in the metal selenide porous framework/graphene composite fibre
The complex method of object be graphene coated metal selenide or metal selenide uniform load on the surface of graphene on one kind or
Two kinds, specifically depending on metal selenide 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 selenide porous framework/graphene composite fibre of various metals selenides.
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 selenide 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 μm, preferably between 40 ~ 50 μm;Graphene oxide dispersion a concentration of 6 ~ 10
mg/mL。
Preferably, the coagulating bath is selected from CaCl2Aqueous solution, ethyl alcohol, the ethanol solution or acetic acid for being saturated potassium hydroxide
Any one in ethyl ester;Wherein, the CaCl2CaCl in aqueous solution2Mass fraction be 5%..
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 ~ 1.5h is calcined, selenium sulphur powder is added to 300 ~ 380 DEG C in rear Temperature fall, calcines 0.5 ~ 1.5h, finally drops naturally
Temperature obtains the metal selenide porous framework/graphene composite fibre;Wherein, the selenium powder is added 0.3 to 1.2 grams.
A kind of porous metals selenizing that the preparation method of metal selenide porous framework/graphene composite fibre is prepared
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 selenides porous framework/graphene composite fibre
Body is driven, metal selenide porous framework/graphene composite fibre is prepared into after calcining.The graphene film surface of the fiber is uniformly attached
Metal selenide.Prepared metal selenide porous framework/graphene composite fibre has porous structure, the composite fibre
The porous structure being assembled by metal selenide nano particle is formed with redox graphene, in the synthesis process, is remained
The structural intergrity of graphene and the metal selenide porous framework obtained as template using MOF crystal, has both graphene and metal
The excellent properties of selenides porous framework can play graphene and more simultaneously in the fields such as sensing, catalysis, energy storage, absorption
The excellent properties of both mesoporous metal selenides, and metal selenide 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 selenide porous framework that template obtains, and has had both graphene and the porous frame of metal selenide
The excellent properties of frame.
Description of the drawings
Fig. 1: Fe-MOF(a,b)Crystal scanning electron microscope (SEM) photograph.
Fig. 2:Porous Fe Se2The scanning electron microscope (SEM) photograph of/graphene composite fibre: FeSe2:rGO=3:2 (a,b)。
Fig. 3:Porous Fe Se2The scanning electron microscope Elemental redistribution spectrogram of/graphene composite fibre.
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 porous metals selenides/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 selenide 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 600 degrees Celsius with 10 degree of rates per minute, calcines one hour, after
Temperature fall is added selenium powder and calcines one hour, last Temperature fall obtains a diameter of 30 microns of metal to 350 degrees Celsius
Selenides porous framework/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. 2(a, b)It is the metallic selenium obtained in embodiment 1
The surface topography of compound porous framework/graphene composite fibre, Fig. 2 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 Se above2, fiber thickness is 30 microns;Fig. 2 b are figures
2a 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 Fe Se2RGO pieces surface is all spread
It is full, and without finding porous Fe Se2Agglomeration intuitively demonstrates porous Fe Se2With rGO pieces by uniform compound, and at
Work(obtains one dimension fibre structure.Fig. 3 SEM Elemental redistribution spectrograms show C element, Se elements, Fe elements in the sample uniform
Distribution, further secondary proof porous Fe Se2In being uniformly distributed for rGO on pieces.
Porous metals selenides/graphene the composite fibre has height as the lithium ion battery that negative material is prepared
Specific capacity, high rate performance and good cyclical stability.It is 100 mA/g, voltage range in current density: 0.01-3.00 V
Test condition under, first circle charging and discharging capacity is respectively up to 750.11 and 1258.6 mAh/g, and coulombic efficiency reaches for the first time
67.61 %.And it has outstanding performance in terms of stability, high rate performance.
Embodiment 2:
A kind of preparation method of metal selenide 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)The preparation of metal selenide porous framework/graphene composite fibre:Oxygen is sequentially added in the centrifuge tube of 5 mL sizes
Graphite alkene DMF solution, Co-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 Co-MOF crystal powders, graphene oxide and Co-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/Co-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;Before fine shape is tieed up again
It drives body to be calcined, specially:First lead to nitrogen, is warming up to 600 degrees Celsius with 10 degree of rates per minute, calcines one hour, after
Temperature fall is added selenium powder and calcines one hour, last Temperature fall obtains a diameter of 35 microns of gold to 350 degrees Celsius
Belong to selenides porous framework/graphene composite fibre.
The lithium ion battery tool that the metal selenide porous framework/graphene composite fibre is prepared as negative material
There are height ratio capacity, high rate performance and good cyclical stability.It is 100 mA/g, voltage range in current density: 0.01-
Under the test condition of 3.00 V, first circle charging and discharging capacity is respectively up to 726.3 and 1228.2 mAh/g, coulombic efficiency for the first time
Up to 67.91%.And it has outstanding performance in terms of stability, high rate performance.
Embodiment 3:
The preparation method of metal selenide porous framework/graphene composite fibre, includes the following steps:In the centrifugation of 5 mL sizes
Graphene oxide DMF solution, Fe-MOF crystal powders, Co-MOF crystal powders are sequentially added in pipe, control the initial of each raw material
Rate of charge is as follows:Graphene oxide solution, 6.7 mg/mL of concentration, graphene oxide sheet lateral dimension are 50 μm;Fe-MOF is brilliant
15 mg of body powder, 15 mg of Co-MOF crystal powders, the throwing of graphene oxide, Fe-MOF crystal powders and Co-MOF crystal powders
It is 4 to put mass ratio:3:3;Gained mixture obtains plural gel, i.e., in persistently mixing 2 min through magnetic agitation under confined conditions
Spinning solution, spinning solution is further through wet spinning, specially:It is solidifying that spinning solution is continuously injected into ethyl acetate by syringe
Gu in bath, then through vacuum filtration, spontaneously drying, obtaining fibrous presoma;Fibrous presoma is calcined again, specially:
First lead to nitrogen, 600 degrees Celsius be warming up to 10 degree rates per minute, calcining one hour, rear Temperature fall to 350 degrees Celsius,
Selenium powder is added to calcine one hour, last Temperature fall obtains a diameter of 35 microns of metal selenide porous framework/graphene
Composite fibre.
The lithium ion battery tool that the metal selenide porous framework/graphene composite fibre is prepared as negative material
There are height ratio capacity, high rate performance and good cyclical stability.It is 100 mA/g, voltage range in current density: 0.01-
Under the test condition of 3.00 V, first circle charging and discharging capacity is respectively up to 743.7 and 1235.4 mAh/g, coulombic efficiency for the first time
Up to 70.12 %.And it has outstanding performance in terms of stability, high rate performance.
Embodiment 4
A kind of preparation method of metal selenide porous framework/graphene composite fibre, includes the following steps:
(1)The preparation of Ni-MOF crystal powders:20 mL deionized waters are added in the beaker that capacity is 50 mL, then, successively
1.3 g Nickel dichloride hexahydrates and 3 g sodium oxalates are added thereto, stirring makes it completely dissolved, and obtains green solution.Separately take one
Capacity is the beaker of 50 mL, and 1.3 g Nickel dichloride hexahydrates are added thereto, so that it is laid in beaker bottom, is then slowly added dropwise
The ethylenediamine solution of 1.5 mL makes it come into full contact with and react with Nickel dichloride hexahydrate, and sample is dark purple at this time.By above-mentioned two
Solution mixing in beaker, magnetic agitation make it completely dissolved, and store 48 h at room temperature.After reaction, low-speed centrifugal(Room
Temperature, 15 min, 4000 rpm), supernatant is removed, then washed, centrifuged 3 times repeatedly with methanol, products therefrom is true through 60 DEG C
Ni-MOF crystal powders are finally obtained after dry 24 h of sky;
(2)The preparation of metal selenide porous framework/graphene composite fibre:Oxygen is sequentially added in the centrifuge tube of 5 mL sizes
Graphite alkene DMF solution, Ni-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 Ni-MOF crystal powders, graphene oxide and Ni-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/Ni-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 600 degrees Celsius with 10 degree of rates per minute, calcines one hour, after
Temperature fall is added selenium powder and calcines one hour, last Temperature fall obtains a diameter of 30 microns of metal to 350 degrees Celsius
Selenides porous framework/graphene composite fibre.
In conclusion can successfully prepare the metal that each component is evenly distributed, appearance structure is controllable by our method
Selenides porous framework/graphene composite fibre, the porous structure which is assembled by metal selenide nano particle
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 metal selenide porous framework/graphene composite fibre, which is characterized in that the porous frame of metal selenide
Frame/graphene composite fibre using MOF crystal powders and graphene oxide by compound obtained fibrous composite as presoma,
It is obtained by calcining.
2. a kind of preparation method of metal selenide porous framework/graphene composite fibre, which is characterized in that including following step
Suddenly:
It takes the graphene oxide dispersion of MOF crystal powders and a concentration of 0.1 ~ 100 mg/mL in mixing under confined conditions, stirs
It is uniform to obtain spinning solution;Wherein, the mass ratio that feeds intake of the MOF crystal powders and graphene oxide is (0.1~10):1;
Above-mentioned spinning solution is obtained into metal selenide porous framework/graphene composite fibre presoma by wet spinning;
By step(2)Described in selenium powder is added in presoma, through 300 ~ 600 DEG C of 1 ~ 20h of calcining, be prepared into a diameter of 20 ~ 50
The composite fibre of micron, i.e., described metal selenide porous framework/graphene composite fibre.
3. a kind of preparation method of metal selenide porous framework/graphene composite fibre according to claim 2, special
Sign is that the graphene oxide dispersion is that graphene oxide/aqueous solution or graphene oxide/n,N-Dimethylformamide are molten
Liquid.
4. a kind of preparation method of metal selenide porous framework/graphene composite fibre according to claim 2, special
Sign is, the composite square of graphene surface and metal selenide in the metal selenide porous framework/graphene composite fibre
Formula be graphene coated metal selenide or metal selenide uniform load on the surface of graphene on one or two.
5. a kind of preparation method of metal selenide 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 selenide porous framework/graphene composite fibre according to claim 2 or 4,
It is characterized in that, the wet spinning includes the following steps:The spinning solution is continuously injected into solidification by syringe
In bath, then through vacuum filtration, spontaneously dries, obtain the metal selenide porous framework/graphene composite fibre presoma.
7. a kind of preparation side of metal selenide porous framework/graphene composite fibre according to claim 2,3 or 6
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 graphene oxide
For sheet, 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 selenide 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 selenide porous framework/graphene composite fibre according to claim 6, special
Sign is, step(3)In, 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, selenium sulphur powder is added to 300 ~ 380 DEG C in rear Temperature fall, calcines 0.5 ~ 1.5 h, last natural
Cooling, obtains the metal selenide porous framework/graphene composite fibre;Wherein, the selenium powder is added 0.3 to 1.2 grams.
10. a kind of porous metals selenizing that the preparation method of metal selenide porous framework/graphene composite fibre is prepared
Application of the object/graphene composite fibre in the energy, environment or flexible device field.
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