CN105789591A - Method for synthesizing graphene/FeSn-nanorod array/graphene composite material of tent type frame structure - Google Patents
Method for synthesizing graphene/FeSn-nanorod array/graphene composite material of tent type frame structure Download PDFInfo
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Abstract
The invention relates to a method for synthesizing a graphene/FeSn-nanorod array/graphene composite material of a tent type frame structure.The method includes the following steps that a hydrothermal method is utilized, the dosage of a surface active agent and the ratio of a precursor are regulated, and a FeSn/rGO seed crystal is synthesized; a seed growth method is utilized, and a FeSn-nanorod array/rGO is obtained; finally, the hydrothermal method is utilized again, a layer of graphene cap is laid on the surface of the FeSn-nanorod array/rGO, and the tent type stable frame structure is formed.Compared with the prior art, the method is simple in process, mild in reaction condition, stable in product appearance, high in purity and convenient and simple in product treatment, has quite high universality and is suitable for industrial production; raw materials are easy to obtain, no catalyst or template is needed, and the price is low; a product has high charging and discharging performance and lithium electric performance of cycling stability, can serve as a lithium ion anode material of high performance and has wide lithium electric application prospect.
Description
Technical field
The invention belongs to alloy/graphite alkene technical field of composite materials, be specifically related to a kind of solvent-thermal process method synthesis
Tent type Graphene/FeSn-nanometer stick array/Graphene (rGO/FeSn-NRsArray/rGO) frame structure.
Background technology
Current era, environment, the energy, material has become as following three big science fields, and lithium ion battery is because of it
Epoch-making meaning is brought to receive much concern across this three big domain variability to world's life.For lithium ion battery negative
The research of material shows, alloy has specific capacity high but volumetric expansion conference causes the problem of cyclical stability difference, graphite
Alkene also has the most easily reunion, capacity low and the fast limitation that decays.And alloy/graphite alkene composite
By the composite construction of Graphene Yu alloy, may obtain and have the excellent of height ratio capacity and high rate during charging-discharging concurrently
Gesture.Therefore, the alloy/graphite alkene composite of composite construction stablize in exploitation becomes and effectively solves that lithium electricity is single to be born
Pole material faces one of main path of various problem.
Owing in kamash alloy, energy density and reversible capability of charging and discharging are had a major impact by the second constituent element, become urgently
The key point that need to consider.Because by the alloying of Sn with proper content inert component, can effectively control in alloy
Serious volumetric expansion (～300%) that stannum occurs during removal lithium embedded and cause specific capacity to decline rapidly.Recently,
For solving an above-mentioned difficult problem, the alloys such as SnNi, SnCo, FeSn have been carried out bearing as lithium ion battery by researcher
The correlational study of pole material.On the other hand, there are some to show about the research of graphene-based composite construction in the recent period, its
Composite construction can obtain higher lithium electrical property than one-component.Graphene has the electricity of excellence, heat and machine
Tool performance, its huge specific surface area and unique layer structure enable to give the stability that composite construction is higher
And fracture toughness.The electrical conductivity of its superelevation can significantly improve charge-discharge velocity thus improve its energy density and reversible appearance
Amount, and, Graphene can provide a stable substrate for its compounding ingredients, prevents activity in charge and discharge process
The reunion of material, meanwhile, activity compounding ingredients is tied by forming metastable framework with the bonding action of Graphene
Structure, thus it is effectively increased the cyclical stability of negative material.In consideration of it, Graphene can as with kamash alloy
Negative material forms the splendid selection of complex lithium cell negative pole material.But, the Sn base alloy currently mainly studied/
Graphene composite material mostly is FeSn, SnNi, SnCo nanoparticle and is dispersed on Graphene, and yet suffers from
Circulation volume is on the low side, the dissatisfactory situation of cyclical stability.Having traced it to its cause, corpuscular type reactive alloys is through one
Reunion is there occurs after the cycle charge-discharge of fixed cycle.Therefore, stable Sn base alloy/graphite alkene compound frame is built
Structure to develop such lithium ion battery negative material significant, be also one have challenge and difficult
Task.
Summary of the invention
Defect that the purpose of the present invention is contemplated to overcome above-mentioned prior art to exist and provide a kind of cost of material low,
Graphene/FeSn-the nanometer of the tent type frame structure that highly versatile, reaction condition are gentle, technique is controlled and easy
The synthetic method of rod array/graphene composite material, the composite structure stability that the method prepares is high, have
The lithium electrical property of higher charge-discharge performance and cyclical stability.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of synthetic method of the Graphene of tent type frame structure/FeSn-nanometer stick array/graphene composite material,
Comprise the following steps:
(1) synthesis of FeSn/ Graphene crystal seed
(1-1) by graphene oxide and surfactant-dispersed in organic solvent, and add inorganic tin salt and
Inorganic molysite, is uniformly mixed；
(1-2) add reducing agent, be transferred in reactor, be heated to 170～190 DEG C and keep 4～6h, then
It is cooled to room temperature, obtains black solid product, this product is washed and obtains FeSn/ Graphene crystalline substance after drying
Kind；
(2) synthesis of FeSn-nanometer stick array/Graphene
(2-1) the FeSn/ Graphene crystal seed obtained is dispersed in organic tin salt and the organic solution of organic iron salt
In, add reproducibility organic solvent, be uniformly mixed；
(2-2) it is transferred in reactor, is heated to 170～190 DEG C and keeps 4～6h, being then cooled to room temperature,
Obtain black solid product, this product is washed and obtains FeSn-nanometer stick array/Graphene after drying；
(3) synthesis of Graphene/FeSn-nanometer stick array/graphene composite material
(3-1) the FeSn-nanometer stick array/Graphene obtained and graphene oxide are disperseed in organic solvent,
Add reducing agent, be uniformly mixed；
(3-2) it is transferred in reactor, is heated to 170～190 DEG C and keeps 4～6h, being then cooled to room temperature,
Obtain black solid product, this product washs and obtains after drying the Graphene of tent type frame structure
/ FeSn-nanometer stick array/graphene composite material.
The reaction that step (1-2) occurs is as follows:
Sn2++2e-=Sn Fe3++3e-=Fe 2Sn+Fe=Sn2Fe GO+2H++2e-=Graphene+H2O
Generate FeSn/ Graphene crystal seed.
The reaction that step (2-2) occurs is as follows:
Sn2++2e-=Sn Fe3++3e-=Fe 2Sn+Fe=Sn2Fe
Product is grown up to FeSn-nanometer stick array/Graphene by FeSn/ Graphene crystal seed.
The reaction that step (3-2) occurs is as follows:
GO+2H++2e-=Graphene+H2O
Product is become Graphene/FeSn-nanometer stick array/Graphene by FeSn-nanometer stick array/Graphene.
Surfactant in step (1-1) is polyvinylpyrrolidone, and organic solvent is triethylene glycol；
Reproducibility organic solvent in step (2-1) is ethylene glycol；
Organic solvent in step (3-1) is ethylene glycol.
Reducing agent in step (1-2) is NaBH4, NaBH4Addition and this step in graphene oxide
The ratio of addition is 0.3～0.5mol:1g；
Reducing agent in step (3-1) is N2H4·H2O, N2H4·H2The addition of O and this step aoxidize stone
The ratio of the addition of ink alkene is 0.15～0.2L:1g.
Described inorganic tin salt is SnCl2·2H2O, described inorganic molysite is FeCl3·6H2O。
Described organic tin salt is stannous oxalate, and described organic iron salt is ferric acetate.
Described graphene oxide uses the aqueous solution of graphene oxide, and the content of graphene oxide is 0.3～0.7
mg/mL。
The reactor that step (1-2), (2-2) and (3-2) uses respectively has teflon-lined not
Rust steel reactor, the charging coefficient of the reactor that step (1-2), (2-2) and (3-2) uses controls respectively
Between 0.6～0.79, owing to graphene oxide uses its aqueous solution, preferred steps (1-2), (2-2) and
(3-2) volume of the addition of the organic solvent of each step and the graphene oxide water solution volume in step (1-1)
Ratio be 3～10:1.
In step (1-1), the mol ratio of inorganic tin salt and inorganic molysite is 1.6～2.4:1, surfactant and oxygen
The mass ratio of functionalized graphene is 140～180:1, and the consumption of graphene oxide and the ratio of inorganic molysite consumption are 25～40
g:1mol。
Preferably, in step (1-1), the mol ratio of inorganic tin salt and inorganic molysite is 2:1.
When the mol ratio of inorganic tin salt and inorganic molysite is 2:1, meet the stoichiometric proportion of reaction, this join
More stable than the thing being synthesized, synthesis condition is easiest to reach.
In the organic solution of step (2-1), solvent is ethanol, and the concentration of organic iron salt is 4～6mmol/L, has
In machine solution, the mol ratio of organic tin salt and organic iron salt is 0.8～1.2:1, in organic iron salt and step (1-1)
The mol ratio of inorganic molysite is 0.3～0.5:1.
Preferably, in the organic solution of step (2-1), the mol ratio of organic tin salt and organic iron salt is 1:1.Should
Proportioning can make result effect optimal, the beneficially growth of nanometer stick array.
Graphene oxide in step (3-1) is 0.8～1.2:1 with the mass ratio of the graphene oxide in step (1-1).
Preferably, the graphene oxide in step (3-1) and the mass ratio of the graphene oxide in step (1-1)
For 1:1.This mass ratio can make product morphology relatively good, and dispersibility is more uniform, it is not easy to reunites.
Product dehydrated alcohol and deionized water are alternately washed repeatedly by described washing process, pass through after washing every time
Centrifugal separation is by solid-liquid separation；
The heating rate of the heating process in step (1-2) is 0.5～2 DEG C/min, the heating in step (2-2)
The heating rate of process is 0.5～2 DEG C/min, and the heating rate of the heating process in step (3-2) is 0.5～2 DEG C
/min。
Heating rate and temperature retention time can produce material impact to result, and heating rate is the slowest, is more conducive to making crystalline substance
Planting particle and grow up to nanometer stick array, therefore it is required that heating rate is slow as far as possible, but the slowest heating rate makes place
Reason overlong time, therefore the present invention uses the heating rate of 0.5～2 DEG C/min.Temperature retention time can not the shortest can not be too
Long, if temperature retention time is the shortest, do not grow alloy bar the most completely；If temperature retention time is oversize, then the alloy grown up to
Rod is the longest but also thin, is unfavorable for the transmission of lithium ion, thus affects lithium electrical property.
In the present invention, the purity of various reagent is all not less than chemical pure.
The present invention utilizes controlled, easy solvent-thermal method, by adjusting heating rate, temperature retention time, surface activity
The factors such as agent consumption, predecessor kind, predecessor proportioning first grow stannum ferroalloy nanometer stick array on Graphene
(FeSn-nanometer stick array), then sprawl a layer graphene thereon and bind, then form a kind of tent by hydro-thermal method
The stable framework of type Graphene/FeSn-nanometer stick array/Graphene.This structure has a following advantage: 1) up and down
The Graphene of bottom play stably in the structure substrate and fast lithium ion conduction effect；2) the ferrum stannum formed closes
In gold rod array structure, ferrum is as electrochemically inactive material, it is possible to effectively alleviate active substance stannum at charge and discharge process
In volumetric expansion；Meanwhile, the most orderly one-dimensional array structure has high structure and electrochemical stability,
In charge and discharge process, structure is anti-caves in and the anti-expansion of anti-agglomeration, and also takes off the process of lithium for embedding lithium and provide volume
Expansion space；3) one-dimentional structure alloy is very beneficial to electronics or the directional transmissions of lithium ion in charge and discharge process, from
And make negative material have comparatively ideal reversible capacity；4) Graphene that top covers then can protect overall knot
The stability of structure, can effectively reduce the generation of side reaction, is effectively improved the stability under high power charging-discharging and ratio
Capacity；The closing overall structure of this Graphene all standing increases the volumetric expansion space of activity Sn further,
It is beneficial to high current charge-discharge cyclical stability and the raising of recycle ratio capacity.
Compared with prior art, the invention have the advantages that
(1) present invention achieves the presoma utilizing common pink salt and iron salt to be reduction reaction, pass through solvent thermal
Synthetic method has synthesized the Graphene/FeSn-nanometer stick array/Graphene with tent type frame structure first
(rGO/FeSn-NRsArray/rGO) composite, provides a kind of new material for Inorganic synthese.
(2) this method has the highest stability to the structure of product.
(3) present invention is respectively adopted simple inorganic salt as reactant, has the strongest versatility.
(4) product prepared by the present invention has the lithium electrical property of higher charge-discharge performance and cyclical stability, can
Using as having high performance ion cathode material lithium, there is the most wide lithium electricity application prospect.
(5) present invention process is simple, and preparation condition is general, and product morphology is stable, purity is high, and product processes
Convenient succinct, it is suitable for commercial production.
Accompanying drawing explanation
Fig. 1 is FeSn-nanometer stick array/rGO SEM photograph under the multiple of 500nm that embodiment 1 prepares；
Fig. 2 is FeSn-nanometer stick array/rGO SEM photograph under the multiple of 250nm that embodiment 1 prepares；
Fig. 3 is the EDS collection of illustrative plates of FeSn-nanometer stick array/rGO that embodiment 1 prepares；
Fig. 4 is the XRD figure spectrum of FeSn-nanometer stick array/rGO that embodiment 1 prepares；
Fig. 5 is that the tent type frame structure rGO/FeSn-NRsArray/rGO composite that embodiment 1 prepares exists
SEM photograph under the multiple of 500nm；
Fig. 6 is that the tent type frame structure rGO/FeSn-NRsArray/rGO composite that embodiment 1 prepares exists
SEM photograph under the multiple of 250nm；
Fig. 7 is the tent type frame structure rGO/FeSn-NRsArray/rGO composite that embodiment 1 prepares
EDS collection of illustrative plates；
Fig. 8 is the tent type frame structure rGO/FeSn-NRsArray/rGO composite that embodiment 1 prepares
XRD figure is composed；
Fig. 9 is the tent type frame structure rGO/FeSn-NRsArray/rGO composite that embodiment 1 prepares
The full spectrum of XPS collection of illustrative plates；
Figure 10 is the tent type frame structure rGO/FeSn-NRsArray/rGO composite that embodiment 1 prepares
The swarming figure of Sn 3d in XPS collection of illustrative plates；
Figure 11 is the tent type frame structure rGO/FeSn-NRsArray/rGO composite that embodiment 1 prepares
Fe 2p figure in XPS collection of illustrative plates；
Figure 12 is the tent type frame structure rGO/FeSn-NRsArray/rGO composite that embodiment 1 prepares
The swarming figure of C 1s in XPS collection of illustrative plates.
Detailed description of the invention
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
A kind of synthetic method of the Graphene of tent type frame structure/FeSn-nanometer stick array/graphene composite material,
Comprise the following steps:
1) preparation of FeSn-nanometer stick array/rGO
The first step, measures GO (graphene oxide) (0.5mg/mL) aqueous solution the most scattered for 2.5ml,
Add polyvinylpyrrolidone (PVP) 0.2g, be then dispersed in 12.5ml triethylene glycol, add 0.075mmol
SnCl2·2H2The FeCl of O and 0.0375mmol3·6H2O makes it to above-mentioned solution, magnetic agitation half an hour
Mix homogeneously.
Second step, then adds 0.5mmol NaBH to mixed solution4, finally above-mentioned solution is transferred to 20ml
In volume teflon-lined stainless steel cauldron, it is heated to the speed of 1 DEG C per minute the most in an oven
180 DEG C, and keep 5 hours.
3rd step, cooling, during until displays temperature is room temperature, collect the black product obtained bottom inner liner of reaction kettle；
To product dehydrated alcohol, deionized water alternately washs, and after centrifugation, repeated washing is repeatedly, produces the most at last
Thing is vacuum dried in vacuum drying oven；The product obtained is FeSn/rGO crystal seed.
4th step, is dispersed in 1.5ml tin oxalate ethanol solution (0.01M) by the FeSn/rGO crystal seed of above-mentioned acquisition
With 1.5ml ferric acetate ethanol solution (0.01M), then 12.5ml ethylene glycol is added to above-mentioned solution；Magnetic force
Stirring half an hour, makes its mix homogeneously；Finally above-mentioned solution is transferred to 20ml volume teflon-lined
In stainless steel cauldron, it is heated to 180 DEG C with the speed of 1 DEG C per minute the most in an oven, and keeps 5 hours.
5th step, cooling, during until displays temperature is room temperature, collect the black product obtained bottom inner liner of reaction kettle；
To product dehydrated alcohol, deionized water alternately washs, and after centrifugation, repeated washing is repeatedly, produces the most at last
Thing is vacuum dried in vacuum drying oven；The product obtained is FeSn-nanometer stick array/rGO.
2) synthesis of tent type frame structure rGO/FeSn-NRsArray/rGO composite
The first step, is dispersed in 2.5ml is dispersed through the FeSn-nanometer stick array/rGO obtained in above-mentioned (3)
Good GO (0.5mg/ml) aqueous solution, then by 12.5ml ethylene glycol and the N of 200 μ L2H4·H2O adds
To above-mentioned solution.
Second step, magnetic agitation half an hour makes its mix homogeneously.Finally above-mentioned solution is transferred to 20ml volume
In teflon-lined stainless steel cauldron, it is heated to the speed of 1 DEG C per minute the most in an oven
180 DEG C, and keep 5 hours.
3rd step, cooling, during until displays temperature is room temperature, collect the black product obtained bottom inner liner of reaction kettle.
To product dehydrated alcohol, deionized water alternately washs, and after centrifugation, repeated washing is repeatedly, obtains tent
Type frame structure rGO/FeSn-NRsArray/rGO composite, product preserves and is dispersed in anhydrous second the most at last
In alcohol.
Fig. 1～2 is that the scanning electron microscope (SEM) of the FeSn-nanometer stick array/rGO of different enlargement ratio is shone
Sheet, it can be seen that SnFe-nanometer stick array is fitly grown on Graphene, occurs in that in Fig. 3 in EDS collection of illustrative plates
The element peak of Fe, Sn and C, indicates the existence of these three kinds of elements, with the raw material type of the metal ion added
It is consistent；In the XRD figure spectrum of Fig. 4, (211), (202), (213) and (002) are that stannum ferrum carbon crystalline state is closed
Golden goes out peak position；Fig. 5～6 is the rGO/FeSn-NRsArray of the tent type frame structure of different enlargement ratio
Scanning electron microscope (SEM) photo of/rGO, it can be seen that cover one above SnFe-nanometer stick array
Layer graphene, defines the frame structure of tent type；Fig. 7 occurs in that Fe, Sn and C in EDS collection of illustrative plates
Element peak, indicates the existence of these three kinds of elements, is consistent with the raw material type of the metal ion added；Fig. 8's
XRD figure spectrum in (211), (202), (213) and (002) be stannum ferrum carbon crystal alloy go out peak position；
Fig. 9 is that the XPS of the rGO/FeSn-NRsArray/rGO of product tent type frame structure composes entirely, occurs in collection of illustrative plates
The peak of Sn, Fe and C, further demonstrates that the existence of these three kinds of elements, and Figure 10 is Sn 3d during XPS composes entirely
The swarming of track, Sn 3d3/2With Sn 3d5/2Go out peak position and show Sn2+And Sn4+、Sn0The existence of valence state；Figure 11
The division peak of Fe 2p track, Fe 2p in entirely composing for XPS3/2With Fe 2p1/2Go out peak position and show Fe3+And Fe0Valency
The existence of state；Figure 12 is the swarming of C 1s track during XPS composes entirely, it can be seen that the C 1s master of 283.0eV
The C of Graphene to be comprised (282.2eV)0Valence state and the C of C=O key functional group (284.5eV)2+Depositing of valence state
?.
Embodiment 2
A kind of synthetic method of the Graphene of tent type frame structure/FeSn-nanometer stick array/graphene composite material,
Comprise the following steps:
1) preparation of FeSn-nanometer stick array/rGO
The first step, measures GO (graphene oxide) (0.3mg/mL) aqueous solution the most scattered for 2.5ml,
Add polyvinylpyrrolidone (PVP) 0.105g, be then dispersed in triethylene glycol, add SnCl2·2H2O and
FeCl3·6H2O makes its mix homogeneously, wherein, SnCl to above-mentioned solution, magnetic agitation half an hour2·2H2O with
FeCl3·6H2The mol ratio of O is 1.6:1, and the consumption of graphene oxide is 25g:1 with the ratio of the consumption of inorganic molysite
mol。
Second step, then adds NaBH to mixed solution4, addition adds adding of graphene oxide with the first step
The ratio entering amount is 0.3mol:1g, finally above-mentioned solution is transferred to teflon-lined stainless steel cauldron
In, it is heated to 170 DEG C with the speed of 0.5 DEG C per minute the most in an oven, and keeps 6 hours, reactor
Charging coefficient controls 0.6.
3rd step, cooling, during until displays temperature is room temperature, collect the black product obtained bottom inner liner of reaction kettle；
To product dehydrated alcohol, deionized water alternately washs, and after centrifugation, repeated washing is repeatedly, produces the most at last
Thing is vacuum dried in vacuum drying oven；The product obtained is FeSn/rGO crystal seed.
4th step, is dispersed in the FeSn/rGO crystal seed of above-mentioned acquisition in the ethanol solution of tin oxalate and ferric acetate,
Then ethylene glycol is added to above-mentioned solution；Magnetic agitation half an hour, makes its mix homogeneously, wherein tin oxalate and second
The ratio of the amount of the material of acid ferrum is 0.8:1, and the concentration of ferric acetate is 6mmol/L, in ferric acetate and the first step
FeCl3·6H2The mol ratio of O is 0.3:1；Finally above-mentioned solution is transferred to teflon-lined rustless steel anti-
Answer in still, be heated to 170 DEG C with the speed of 0.5 DEG C per minute the most in an oven, and keep 6 hours, reaction
The charging coefficient of still controls 0.6.
5th step, cooling, during until displays temperature is room temperature, collect the black product obtained bottom inner liner of reaction kettle；
To product dehydrated alcohol, deionized water alternately washs, and after centrifugation, repeated washing is repeatedly, produces the most at last
Thing is vacuum dried in vacuum drying oven；The product obtained is FeSn-nanometer stick array/rGO.
2) synthesis of tent type frame structure rGO/FeSn-NRsArray/rGO composite
The first step, is dispersed in the most scattered GO by the FeSn-nanometer stick array/rGO obtained in above-mentioned (3)
(0.3mg/ml) aqueous solution, then by ethylene glycol and N2H4·H2O adds to above-mentioned solution, and wherein this step adds
The GO entered is 1.2:1 with the mass ratio of the GO added when producing FeSn-nanometer stick array/rGO.
Second step, magnetic agitation half an hour makes its mix homogeneously.Finally above-mentioned solution is transferred to politef
In the stainless steel cauldron of liner, the charging coefficient of reactor controls 0.6, the most in an oven with per minute
The speed of 0.5 DEG C is heated to 170 DEG C, and keeps 6 hours.
3rd step, cooling, during until displays temperature is room temperature, collect the black product obtained bottom inner liner of reaction kettle.
To product dehydrated alcohol, deionized water alternately washs, and after centrifugation, repeated washing is repeatedly, obtains tent
Type frame structure rGO/FeSn-NRsArray/rGO composite, product preserves and is dispersed in anhydrous second the most at last
In alcohol.
Embodiment 3
A kind of synthetic method of the Graphene of tent type frame structure/FeSn-nanometer stick array/graphene composite material,
Comprise the following steps:
1) preparation of FeSn-nanometer stick array/rGO
The first step, measures GO (graphene oxide) (0.7mg/mL) aqueous solution the most scattered for 2.5ml,
Add polyvinylpyrrolidone (PVP) 0.315g, be then dispersed in triethylene glycol, add SnCl2·2H2O and
FeCl3·6H2O makes its mix homogeneously, wherein, SnCl to above-mentioned solution, magnetic agitation half an hour2·2H2O with
FeCl3·6H2The mol ratio of O is 2.4:1, and the consumption of graphene oxide is 40g:1 with the ratio of the consumption of inorganic molysite
mol。
Second step, then adds NaBH to mixed solution4, addition adds adding of graphene oxide with the first step
The ratio entering amount is 0.5mol:1g, finally above-mentioned solution is transferred to teflon-lined stainless steel cauldron
In, it is heated to 190 DEG C with the speed of 2 DEG C per minute the most in an oven, and keeps 4 hours, adding of reactor
Material coefficient controls 0.79.
3rd step, cooling, during until displays temperature is room temperature, collect the black product obtained bottom inner liner of reaction kettle；
To product dehydrated alcohol, deionized water alternately washs, and after centrifugation, repeated washing is repeatedly, produces the most at last
Thing is vacuum dried in vacuum drying oven；The product obtained is FeSn/rGO crystal seed.
4th step, is dispersed in the FeSn/rGO crystal seed of above-mentioned acquisition in the ethanol solution of tin oxalate and ferric acetate,
Then ethylene glycol is added to above-mentioned solution；Magnetic agitation half an hour, makes its mix homogeneously, wherein tin oxalate and second
The ratio of the amount of the material of acid ferrum is 1.2:1, and the concentration of ferric acetate is 4mmol/L, in ferric acetate and the first step
FeCl3·6H2The mol ratio of O is 0.5:1；Finally above-mentioned solution is transferred to teflon-lined rustless steel anti-
Answer in still, be heated to 190 DEG C with the speed of 2 DEG C per minute the most in an oven, and keep 4 hours, reactor
Charging coefficient control 0.79.
5th step, cooling, during until displays temperature is room temperature, collect the black product obtained bottom inner liner of reaction kettle；
Product is used anhydrous second, and deionized water alternately washs, and after centrifugation, repeated washing is repeatedly, the most at last product
Vacuum drying oven is vacuum dried；The product obtained is FeSn-nanometer stick array/rGO.
2) synthesis of tent type frame structure rGO/FeSn-NRsArray/rGO composite
The first step, is dispersed in the most scattered GO by the FeSn-nanometer stick array/rGO obtained in above-mentioned (3)
(0.7mg/ml) aqueous solution, then by ethylene glycol and N2H4·H2O adds to above-mentioned solution, and wherein this step adds
The GO entered is 0.8:1 with the mass ratio of the GO added when producing FeSn-nanometer stick array/rGO.
Second step, magnetic agitation half an hour makes its mix homogeneously.Finally above-mentioned solution is transferred to politef
In the stainless steel cauldron of liner, the charging coefficient of reactor controls 0.79, the most in an oven with 2 DEG C per minute
Speed be heated to 190 DEG C, and keep 4 hours.
3rd step, cooling, during until displays temperature is room temperature, collect the black product obtained bottom inner liner of reaction kettle.
To product dehydrated alcohol, deionized water alternately washs, and after centrifugation, repeated washing is repeatedly, obtains tent
Type frame structure rGO/FeSn-NRsArray/rGO composite, product preserves and is dispersed in anhydrous second the most at last
In alcohol.
The above-mentioned description to embodiment is to be understood that and apply this for ease of those skilled in the art
Invention.These embodiments obviously easily can be made various amendment by person skilled in the art, and handle exists
The General Principle of this explanation is applied in other embodiments without through performing creative labour.Therefore, the present invention is not
It is limited to embodiment here, in the amendment made without departing from the scope of the invention all the guarantor of the present invention
Within the scope of protecting.
Claims (10)
1. the synthesis side of the Graphene of a tent type frame structure/FeSn-nanometer stick array/graphene composite material
Method, it is characterised in that comprise the following steps:
(1) synthesis of FeSn/ Graphene crystal seed
(1-1) by graphene oxide and surfactant-dispersed in organic solvent, and add inorganic tin salt and
Inorganic molysite, is uniformly mixed；
(1-2) add reducing agent, be transferred in reactor, be heated to 170～190 DEG C and keep 4～6h, then
It is cooled to room temperature, obtains black solid product, this product is washed and obtains FeSn/ Graphene crystalline substance after drying
Kind；
(2) synthesis of FeSn-nanometer stick array/Graphene
(2-1) the FeSn/ Graphene crystal seed obtained is dispersed in organic tin salt and the organic solution of organic iron salt
In, add reproducibility organic solvent, be uniformly mixed；
(2-2) it is transferred in reactor, is heated to 170～190 DEG C and keeps 4～6h, being then cooled to room temperature,
Obtain black solid product, this product is washed and obtains FeSn-nanometer stick array/Graphene after drying；
(3) synthesis of Graphene/FeSn-nanometer stick array/graphene composite material
(3-1) the FeSn-nanometer stick array/Graphene obtained and graphene oxide are disperseed in organic solvent,
Add reducing agent, be uniformly mixed；
(3-2) it is transferred in reactor, is heated to 170～190 DEG C and keeps 4～6h, being then cooled to room temperature,
Obtain black solid product, this product washs and obtains after drying the Graphene of tent type frame structure
/ FeSn-nanometer stick array/graphene composite material.
The Graphene of tent type frame structure the most according to claim 1/FeSn-nanometer stick array/Graphene
The synthetic method of composite, it is characterised in that
Surfactant in step (1-1) is polyvinylpyrrolidone, and organic solvent is triethylene glycol；
Reproducibility organic solvent in step (2-1) is ethylene glycol；
Organic solvent in step (3-1) is ethylene glycol.
The Graphene of tent type frame structure the most according to claim 1/FeSn-nanometer stick array/Graphene
The synthetic method of composite, it is characterised in that
Reducing agent in step (1-2) is NaBH4, NaBH4Addition and this step in graphene oxide
The ratio of addition is 0.3～0.5mol:1g；
Reducing agent in step (3-1) is N2H4·H2O, N2H4·H2The addition of O and this step aoxidize stone
The ratio of the addition of ink alkene is 0.15～0.2L:1g.
The Graphene of tent type frame structure the most according to claim 1/FeSn-nanometer stick array/Graphene
The synthetic method of composite, it is characterised in that described inorganic tin salt is SnCl2·2H2O, described nothing
Machine iron salt is FeCl3·6H2O。
The Graphene of tent type frame structure the most according to claim 1/FeSn-nanometer stick array/Graphene
The synthetic method of composite, it is characterised in that described organic tin salt is stannous oxalate, described Organic Iron
Salt is ferric acetate.
The Graphene of tent type frame structure the most according to claim 1/FeSn-nanometer stick array/Graphene
The synthetic method of composite, it is characterised in that described graphene oxide uses the aqueous solution of graphene oxide,
The content of graphene oxide is 0.3～0.7mg/mL.
The Graphene of tent type frame structure the most according to claim 1/FeSn-nanometer stick array/Graphene
The synthetic method of composite, it is characterised in that in step (1-1) inorganic tin salt and inorganic molysite mole
Ratio is 1.6～2.4:1, and surfactant is 140～180:1 with the mass ratio of graphene oxide, the use of graphene oxide
Measuring the ratio with inorganic molysite consumption is 25～40g:1mol.
The Graphene of tent type frame structure the most according to claim 1/FeSn-nanometer stick array/Graphene
The synthetic method of composite, it is characterised in that in the organic solution of step (2-1), solvent is ethanol, has
The concentration of machine iron salt is 4～6mmol/L, and in organic solution, the mol ratio of organic tin salt and organic iron salt is
0.8～1.2:1, organic iron salt is 0.3～0.5:1 with the mol ratio of inorganic molysite in step (1-1).
The Graphene of tent type frame structure the most according to claim 1/FeSn-nanometer stick array/Graphene
The synthetic method of composite, it is characterised in that in the graphene oxide in step (3-1) and step (1-1)
The mass ratio of graphene oxide be 0.8～1.2:1.
The Graphene of tent type frame structure the most according to claim 1/FeSn-nanometer stick array/Graphene
The synthetic method of composite, it is characterised in that
Product dehydrated alcohol and deionized water are alternately washed repeatedly by described washing process, pass through after washing every time
Centrifugal separation is by solid-liquid separation；
The heating rate of the heating process in step (1-2) is 0.5～2 DEG C/min, the heating in step (2-2)
The heating rate of process is 0.5～2 DEG C/min, and the heating rate of the heating process in step (3-2) is 0.5～2 DEG C
/min。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107887593A (en) * | 2017-11-20 | 2018-04-06 | 长沙理工大学 | A kind of preparation method of graphene CoFeSn composites |
| CN111916719A (en) * | 2020-08-17 | 2020-11-10 | 戴知 | Lithium ion battery cathode material and preparation method and application thereof |
| CN112694084A (en) * | 2020-12-11 | 2021-04-23 | 上海交通大学 | Graphene nanoribbon device array and preparation system and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101702377A (en) * | 2009-10-29 | 2010-05-05 | 彩虹集团公司 | Zinc oxide/titanium dioxide hybrid electrode and preparation method thereof |
| CN102332572A (en) * | 2011-09-21 | 2012-01-25 | 广东达之邦新能源技术有限公司 | Anode material and manufacturing method thereof as well as lithium ion battery and negative plate thereof |
| CN102522543A (en) * | 2011-12-15 | 2012-06-27 | 清华大学 | Method for preparing nanometer compound of tin disulfide-graphene |
| CN102780004A (en) * | 2012-08-16 | 2012-11-14 | 上海中聚佳华电池科技有限公司 | Manganese ferrate/graphene composite and method for preparing same |
| CN102903891A (en) * | 2012-10-12 | 2013-01-30 | 上海中聚佳华电池科技有限公司 | Negative material SnOxS2-x/graphene composite for lithium ion battery and preparation method thereof |
| CN103050661A (en) * | 2012-12-12 | 2013-04-17 | 清华大学深圳研究生院 | Lithium ion battery cathode material compounded with graphene and preparation method thereof |
| CN103094564A (en) * | 2013-01-16 | 2013-05-08 | 天津大学 | Method for preparing composite nano material filled with lithium iron phosphate between graphene layers |
| CN104064739A (en) * | 2014-07-02 | 2014-09-24 | 长沙国容新能源有限公司 | Tin cobalt alloy/ graphene composite material and preparation method thereof |
| CN104300151A (en) * | 2014-10-13 | 2015-01-21 | 同济大学 | Preparation method of porous carbon ball-loaded M-Sn alloy nano particle composite material |
-
2016
- 2016-04-13 CN CN201610227883.9A patent/CN105789591B/en not_active Expired - Fee Related
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101702377A (en) * | 2009-10-29 | 2010-05-05 | 彩虹集团公司 | Zinc oxide/titanium dioxide hybrid electrode and preparation method thereof |
| CN102332572A (en) * | 2011-09-21 | 2012-01-25 | 广东达之邦新能源技术有限公司 | Anode material and manufacturing method thereof as well as lithium ion battery and negative plate thereof |
| CN102522543A (en) * | 2011-12-15 | 2012-06-27 | 清华大学 | Method for preparing nanometer compound of tin disulfide-graphene |
| CN102780004A (en) * | 2012-08-16 | 2012-11-14 | 上海中聚佳华电池科技有限公司 | Manganese ferrate/graphene composite and method for preparing same |
| CN102903891A (en) * | 2012-10-12 | 2013-01-30 | 上海中聚佳华电池科技有限公司 | Negative material SnOxS2-x/graphene composite for lithium ion battery and preparation method thereof |
| CN103050661A (en) * | 2012-12-12 | 2013-04-17 | 清华大学深圳研究生院 | Lithium ion battery cathode material compounded with graphene and preparation method thereof |
| CN103094564A (en) * | 2013-01-16 | 2013-05-08 | 天津大学 | Method for preparing composite nano material filled with lithium iron phosphate between graphene layers |
| CN104064739A (en) * | 2014-07-02 | 2014-09-24 | 长沙国容新能源有限公司 | Tin cobalt alloy/ graphene composite material and preparation method thereof |
| CN104300151A (en) * | 2014-10-13 | 2015-01-21 | 同济大学 | Preparation method of porous carbon ball-loaded M-Sn alloy nano particle composite material |
Non-Patent Citations (1)
| Title |
|---|
| YAYE ET AL.: ""Facile Synthesis of grapheme supported FeSn2 nanocrystals with enhanced Li-stroage capacity"", 《RSC ADV.》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107887593A (en) * | 2017-11-20 | 2018-04-06 | 长沙理工大学 | A kind of preparation method of graphene CoFeSn composites |
| CN111916719A (en) * | 2020-08-17 | 2020-11-10 | 戴知 | Lithium ion battery cathode material and preparation method and application thereof |
| CN112694084A (en) * | 2020-12-11 | 2021-04-23 | 上海交通大学 | Graphene nanoribbon device array and preparation system and preparation method thereof |
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|---|---|
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