CN105789591B - The synthetic method of the graphene of tent type frame structure/FeSn- nanometer stick arrays/graphene composite material - Google Patents
The synthetic method of the graphene of tent type frame structure/FeSn- nanometer stick arrays/graphene composite material Download PDFInfo
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Abstract
The present invention relates to a kind of synthetic methods of graphene of tent type frame structure/FeSn nanometer stick arrays/graphene composite material, include the following steps：Using hydro-thermal method, regulates and controls dosage of surfactant and predecessor proportioning, synthesized FeSn/rGO crystal seeds, then, by seed mediated growth method, FeSn nanometer stick arrays/rGO is obtained, finally again by hydro-thermal method, a layer graphene is sprawled in the above and is bound, a kind of stable framework of tent type is formed.Compared with prior art, present invention process is simple, and preparation condition is mild, and product morphology is stable, purity is high, and product processing facilitates succinct, has very strong versatility, is suitable for industrial production；Raw material are easy to get, and do not need catalyst and template, cheap；Product has the lithium electrical property of higher charge-discharge performance and cyclical stability, can be used as ion cathode material lithium with high performance, there is wide lithium electricity application prospect.
Description
Technical field
The invention belongs to alloy/graphite alkene technical field of composite materials, and in particular to a kind of solvent-thermal process method synthesis account
Paulin type graphene/FeSn- nanometer stick arrays/graphene (rGO/FeSn-NRsArray/rGO) frame structure.
Background technology
Current era, environment, the energy, material have become the following three big science fields, and lithium ion battery because its across
This three big domain variability brings epoch-making meaning to world's life and is concerned.For the research of lithium ion battery negative material
It has been shown that, alloy have the problem that specific capacity height but volume expansion conference lead to cyclical stability difference, graphene also to have in practical application
In easily reunite, capacity is low and the fast limitation of decaying.And alloy/graphite alkene composite material is by the composite junction of graphene and alloy
Structure may obtain the advantage for having both height ratio capacity and high rate during charging-discharging.Therefore, develop stablize composite construction alloy/
Graphene composite material, which becomes, effectively solves the problems, such as that the single negative material of lithium electricity faces various one of main paths.
Since the second constituent element has a major impact energy density and reversible capability of charging and discharging in kamash alloy, become there is an urgent need for
The key point of consideration.Because by the alloying of Sn and proper content inert component, tin can be effectively controlled in alloy in removal lithium embedded
The serious volume expansion (~300%) that occurs in the process and cause specific capacity to decline rapidly.Recently, it to solve above-mentioned problem, grinds
The person of studying carefully has carried out the alloys such as SnNi, SnCo, FeSn the correlative study as lithium ion battery negative material.On the other hand,
There are some that can obtain higher compared with one-component about the studies have shown that of graphene-based composite construction its composite construction in the recent period
Lithium electrical property.There is graphene excellent electricity, heat and mechanical performance, its huge specific surface area and unique layer structure to make
Can assign the higher stability of composite construction and fracture toughness.The conductivity of its superelevation can significantly improve charge-discharge velocity from
And its energy density and reversible capacity are improved, also, graphene can provide a stable substrate for its compounding ingredients, prevent
The reunion of active material in charge and discharge process, meanwhile, active compounding ingredients are formed relatively steady by the bonding action with graphene
Fixed frame structure, to effectively increase the cyclical stability of negative material.In consideration of it, graphene can be closed as with tinbase
Golden negative material forms the splendid selection of compound lithium cell negative pole material.However, the Sn based alloys/graphene mainly studied at present is multiple
Condensation material is mostly that FeSn, SnNi, SnCo nano-particle are dispersed on graphene, and there are still circulation volume is relatively low, cycle
The not ideal enough situation of stability.Tracing it to its cause has, and corpuscular type reactive alloys occur after the cycle charge-discharge of some cycles
Reunite.Therefore, stable Sn based alloys/graphene compound frame structure is built to developing such lithium ion battery negative material
Be of great significance and one have challenge and difficult Task.
Invention content
It is low, logical that it is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of costs of material
With property is strong, reaction condition is mild, technique is controllable and the graphene of easy tent type frame structure/FeSn- nanometer stick arrays/stone
The synthetic method of black alkene composite material, composite structure stability made from this method is high, has higher charge-discharge performance
With the lithium electrical property of 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 arrays/graphene composite material,
Include the following steps：
(1) synthesis of FeSn/ graphenes crystal seed
In organic solvent, and inorganic tin salt and inorganic is added in graphene oxide and surfactant-dispersed by (1-1)
Molysite is uniformly mixed；
Reducing agent is added in (1-2), is transferred in reaction kettle, is heated to 170~190 DEG C and keeps 4~6h, is subsequently cooled to
Room temperature obtains black solid product, is washed to the product and obtains FeSn/ graphene crystal seeds after being dried；
(2) synthesis of FeSn- nanometer stick arrays/graphene
Obtained FeSn/ graphene crystal seeds are dispersed in the organic solution of organic tin salt and organic molysite by (2-1), are added
Enter reproducibility organic solvent, is uniformly mixed；
(2-2) is transferred in reaction kettle, is heated to 170~190 DEG C and is kept 4~6h, then cools to room temperature, obtain black
Color solid product washs the product and obtains FeSn- nanometer stick arrays/graphene after being dried；
(3) synthesis of graphene/FeSn- nanometer stick arrays/graphene composite material
Obtained FeSn- nanometer stick arrays/graphene and graphene oxide are disperseed in organic solvent, to be added by (3-1)
Reducing agent is uniformly mixed；
(3-2) is transferred in reaction kettle, is heated to 170~190 DEG C and is kept 4~6h, then cools to room temperature, obtain black
Color solid product washs the product and obtains graphene/FeSn- nanometer rods battle arrays of tent type frame structure after being dried
Row/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 seeds.
The reaction that step (2-2) occurs is as follows：
Sn2++2e-=Sn Fe3++3e-=Fe 2Sn+Fe=Sn2Fe
Product grows up to FeSn- nanometer stick arrays/graphene by FeSn/ graphene crystal seeds.
The reaction that step (3-2) occurs is as follows：
GO+2H++2e-=Graphene+H2O
Product becomes graphene/FeSn- nanometer stick arrays/graphene by FeSn- nanometer stick arrays/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 the step in graphene oxide addition it
Than for 0.3~0.5mol:1g；
Reducing agent in step (3-1) is N2H4·H2O, N2H4·H2The addition of O and graphene oxide in the step
The ratio between addition is 0.15~0.2L:1g.
The inorganic tin salt is SnCl2·2H2O, the inorganic molysite are FeCl3·6H2O。
Organic tin salt is stannous oxalate, and organic molysite is ferric acetate.
The graphene oxide uses the aqueous solution of graphene oxide, and the content of graphene oxide is 0.3~0.7mg/
mL。
The reaction kettle that step (1-2), (2-2) and (3-2) uses is respectively the stainless steel with polytetrafluoroethyllining lining
The charging coefficient of reaction kettle, the reaction kettle that step (1-2), (2-2) and (3-2) uses controls between 0.6~0.79 respectively,
Since graphene oxide is using its aqueous solution, the organic solvent of preferred steps (1-2), (2-2) and (3-2) each step
The volume of addition is 3~10 with the ratio between the graphene oxide water solution volume in step (1-1):1.
The molar ratio of inorganic tin salt and inorganic molysite is 1.6~2.4 in step (1-1):1, surfactant with oxidation
The mass ratio of graphene is 140~180:1, the dosage of graphene oxide and the ratio of inorganic molysite dosage are 25~40g:1mol.
Preferably, the molar ratio of inorganic tin salt and inorganic molysite is 2 in step (1-1):1.
When the molar ratio of inorganic tin salt and inorganic molysite is 2:When 1, meet the stoichiometric ratio of reaction, this proportioning is closed
Mutually most stable at object out, synthesis condition is easiest to reach.
In the organic solution of step (2-1), solvent is ethyl alcohol, a concentration of 4~6mmol/L of organic molysite, organic solution
In the molar ratio of organic tin salt and organic molysite be 0.8~1.2:1, organic molysite rubs with inorganic molysite in step (1-1)
You are than being 0.3~0.5:1.
Preferably, the molar ratio of organic tin salt and organic molysite is 1 in the organic solution of step (2-1):1.The proportioning
Result effect can be made best, be conducive to the growth of nanometer stick array.
The mass ratio of graphene oxide in step (3-1) and the graphene oxide in step (1-1) is 0.8~1.2:1.
Preferably, the mass ratio of the graphene oxide in step (3-1) and the graphene oxide in step (1-1) is 1:1.
The mass ratio can make product morphology relatively good, and dispersibility is more uniform, it is not easy to reunite.
The washing process product absolute ethyl alcohol and deionized water are alternately washed it is multiple, each time after washing by from
Centrifugal separation will be separated by solid-liquid separation；
The heating rate of heating process in step (1-2) is 0.5~2 DEG C/min, the heating process in step (2-2)
Heating rate 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 soaking time can have an important influence on result, and heating rate is slower, more be conducive to make crystal seed
Particle grows up to nanometer stick array, therefore it is required that heating rate is as slow as possible, but excessively slow heating rate makes processing time mistake
It is long, therefore the present invention uses the heating rate of 0.5~2 DEG C/min.Soaking time cannot it is too short can not be too long, if soaking time
It is too short, then do not grow alloy bar completely；If soaking time is too long, the alloy bar grown up to was not only long but also thin, was unfavorable for lithium ion
Transmission, to influence lithium electrical property.
It is pure to be not less than chemistry for the purity of various reagents in the present invention.
The present invention is used using controllable, easy solvent-thermal method by adjusting heating rate, soaking time, surfactant
The factors such as amount, forerunner's species, predecessor proportioning first grow (FeSn- nanometers of tin ferroalloy nanometer stick array on graphene
Stick array), then a layer graphene is sprawled on it and is bound, then a kind of tent type graphene/FeSn- nanometers is formed by hydro-thermal method
The stable framework of stick array/graphene.The structure has following advantage：1) graphene of bottom plays surely in the structure up and down
Determine the effect of substrate and fast lithium ion conduction；2) in the ferro-tin alloy stick array structure formed, iron is as electrochemicaUy inert object
Volume expansion of the active material tin in charge and discharge process can be effectively relieved in matter；Meanwhile close orderly one-dimensional array structure
There are high structure and electrochemical stability, structure is anti-in charge and discharge process caves in and the anti-expansion of anti-agglomeration, and is also
The process that embedding lithium takes off lithium provides volume expansion space；3) one-dimentional structure alloy be very beneficial in charge and discharge process electronics or lithium from
The directional transmissions of son, so that negative material has comparatively ideal reversible capacity；4) graphene of top covering can then be protected
Protect integrally-built stability, the generation of side reaction can be effectively reduced, effectively improve stability under high power charging-discharging and
Specific capacity；The closing overall structure of this graphene all standing further increases the volume expansion space of active Sn, is conducive to big
The raising of current charging and discharging cyclical stability and cycle specific capacity.
Compared with prior art, the present invention has the following advantages：
(1) present invention is realized using the presoma that common pink salt and molysite are reduction reaction, passes through solvent-thermal process
Method has synthesized graphene/FeSn- nanometer stick arrays/graphene (rGO/FeSn- with tent type frame structure for the first time
NRsArray/rGO) composite material provides a kind of new material for Inorganic synthese.
(2) this method has very high stability to the structure of product.
(3) simple inorganic salts are respectively adopted as reactant in the present invention, have very strong versatility.
(4) product prepared by the present invention has the lithium electrical property of higher charge-discharge performance and cyclical stability, Ke Yizuo
For ion cathode material lithium with high performance, there is more 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 processing facilitates letter
It is clean, it is suitable for industrial production.
Description of the drawings
Fig. 1 is FeSn- nanometer stick arrays/SEM photographs of the rGO under the multiple of 500nm made from embodiment 1；
Fig. 2 is FeSn- nanometer stick arrays/SEM photographs of the rGO under the multiple of 250nm made from embodiment 1；
Fig. 3 is the EDS collection of illustrative plates of FeSn- nanometer stick arrays/rGO made from embodiment 1；
Fig. 4 is the XRD spectrum of FeSn- nanometer stick arrays/rGO made from embodiment 1；
Fig. 5 is tent type frame structure rGO/FeSn-NRsArray/rGO composite materials made from embodiment 1 in 500nm
Multiple under SEM photograph；
Fig. 6 is tent type frame structure rGO/FeSn-NRsArray/rGO composite materials made from embodiment 1 in 250nm
Multiple under SEM photograph；
Fig. 7 is the EDS figures of tent type frame structure rGO/FeSn-NRsArray/rGO composite materials made from embodiment 1
Spectrum；
Fig. 8 is the XRD diagram of tent type frame structure rGO/FeSn-NRsArray/rGO composite materials made from embodiment 1
Spectrum；
Fig. 9 is the XPS figures of tent type frame structure rGO/FeSn-NRsArray/rGO composite materials made from embodiment 1
The full spectrum of spectrum；
Figure 10 is the XPS figures of tent type frame structure rGO/FeSn-NRsArray/rGO composite materials made from embodiment 1
The swarming figure of Sn 3d in spectrum；
Figure 11 is the XPS figures of tent type frame structure rGO/FeSn-NRsArray/rGO composite materials made from embodiment 1
Fe 2p figures in spectrum；
Figure 12 is the XPS figures of tent type frame structure rGO/FeSn-NRsArray/rGO composite materials made from embodiment 1
The swarming figure of C 1s in spectrum.
Specific implementation mode
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 arrays/graphene composite material,
Include the following steps：
1) preparation of FeSn- nanometer stick arrays/rGO
The first step measures 2.5ml scattered GO (graphene oxide) (0.5mg/mL) aqueous solutions, polyethylene is added
Pyrrolidones (PVP) 0.2g, is then dispersed in 12.5ml triethylene glycols, the SnCl of 0.075mmol is added2·2H2O and
The FeCl of 0.0375mmol3·6H2For O to above-mentioned solution, magnetic agitation half an hour makes it be uniformly mixed.
Then 0.5mmol NaBH are added to mixed solution in second step4, above-mentioned solution is finally transferred to 20ml volumes and is gathered
In the stainless steel cauldron of tetrafluoroethene liner, 180 DEG C then are heated to 1 DEG C of speed per minute in an oven, and keep 5
Hour.
Third walks, cooling, until when displays temperature is room temperature, collects the black product that inner liner of reaction kettle bottom obtains；It is right
Product absolute ethyl alcohol, deionized water are alternately washed, and are washed repeatedly repeatedly after centrifugation, are finally done product in vacuum
It is dried in vacuo in dry case；Obtained product is FeSn/rGO crystal seeds.
4th step, by the FeSn/rGO crystal seeds of above-mentioned acquisition be dispersed in 1.5ml tin oxalates ethanol solution (0.01M) and
Then 12.5ml ethylene glycol is added to above-mentioned solution for 1.5ml ferric acetates ethanol solution (0.01M)；Magnetic agitation half an hour
It is set to be uniformly mixed；Finally above-mentioned solution is transferred in the stainless steel cauldron of 20ml volume polytetrafluoroethyllining linings, then
180 DEG C are heated to 1 DEG C of rate per minute in an oven, and is kept for 5 hours.
5th step, it is cooling, until when displays temperature is room temperature, collect the black product that inner liner of reaction kettle bottom obtains；It is right
Product absolute ethyl alcohol, deionized water are alternately washed, and are washed repeatedly repeatedly after centrifugation, are finally done product in vacuum
It is dried in vacuo in dry case；Obtained product is FeSn- nanometer stick arrays/rGO.
2) synthesis of tent type frame structure rGO/FeSn-NRsArray/rGO composite materials
FeSn- nanometer stick arrays/the rGO obtained in above-mentioned (3) is dispersed in 2.5ml scattered GO by the first step
(0.5mg/ml) aqueous solution, then by the N of 12.5ml ethylene glycol and 200 μ L2H4·H2O is added to above-mentioned solution.
Second step, magnetic agitation half an hour make it be uniformly mixed.Above-mentioned solution is finally transferred to 20ml volumes poly- four
In the stainless steel cauldron of vinyl fluoride liner, 180 DEG C then are heated to 1 DEG C of rate per minute in an oven, and holding 5 is small
When.
Third walks, cooling, until when displays temperature is room temperature, collects the black product that inner liner of reaction kettle bottom obtains.It is right
Product absolute ethyl alcohol, deionized water are alternately washed, and are washed repeatedly repeatedly after centrifugation, are obtained tent type frame structure
Product is finally preserved and is dispersed in absolute ethyl alcohol by rGO/FeSn-NRsArray/rGO composite materials.
Fig. 1~2 are scanning electron microscope (SEM) photo of FeSn- nanometer stick arrays/rGO of different enlargement ratios, can
To find out, SnFe- nanometer stick arrays are fitly grown on graphene, occur the element of Fe, Sn and C in Fig. 3 in EDS collection of illustrative plates
Peak shows the presence of three kinds of elements, is consistent with the raw material type of the metal ion of addition；(211) in the XRD spectrum of Fig. 4,
(202), (213) and (002) go out peak position for tin iron carbon crystal alloy；Fig. 5~6 are the tent type of different enlargement ratios
Scanning electron microscope (SEM) photo of the rGO/FeSn-NRsArray/rGO of frame structure, it can be seen that SnFe- nanometer rods
A layer graphene is covered above array, forms the frame structure of tent type；There is Fe, Sn and C in EDS collection of illustrative plates in Fig. 7
Element peak, show the presence of three kinds of elements, be consistent with the raw material type of the metal ion of addition；In the XRD spectrum of Fig. 8
(211), (202), (213) and (002) go out peak position for tin iron carbon crystal alloy；Fig. 9 is product tent type frame knot
The XPS of the rGO/FeSn-NRsArray/rGO of structure is composed entirely, occurs the peak of Sn, Fe and C in collection of illustrative plates, further demonstrates that this three kinds
The presence of element, Figure 10 are the swarming of Sn 3d tracks during XPS is composed entirely, Sn 3d3/2With Sn 3d5/2Go out peak position and shows Sn2+With
Sn4+、Sn0The presence of valence state；Figure 11 is the division peak of Fe 2p tracks during XPS is composed entirely, Fe 2p3/2With Fe 2p1/2Go out peak position table
Bright Fe3+And Fe0The presence of valence state；Figure 12 is the swarming of C 1s tracks during XPS is composed entirely, it can be seen that the C 1s of 283.0eV are main
Include the C of graphene (282.2eV)0The C of valence state and C=O keys functional group (284.5eV)2+The presence of valence state.
Embodiment 2
A kind of synthetic method of the graphene of tent type frame structure/FeSn- nanometer stick arrays/graphene composite material,
Include the following steps：
1) preparation of FeSn- nanometer stick arrays/rGO
The first step measures 2.5ml scattered GO (graphene oxide) (0.3mg/mL) aqueous solutions, polyethylene is added
Pyrrolidones (PVP) 0.105g, is then dispersed in triethylene glycol, and SnCl is added2·2H2O and FeCl3·6H2O is to above-mentioned molten
Liquid, magnetic agitation half an hour make it be uniformly mixed, wherein SnCl2·2H2O and FeCl3·6H2The molar ratio of O is 1.6:1,
The ratio of the dosage of graphene oxide and the dosage of inorganic molysite is 25g:1mol.
Then NaBH is added to mixed solution in second step4, addition and the first step be added graphene oxide addition it
Than for 0.3mol:Above-mentioned solution is finally transferred in the stainless steel cauldron of polytetrafluoroethyllining lining, then in an oven by 1g
170 DEG C are heated to 0.5 DEG C of speed per minute, and is kept for 6 hours, the charging coefficient of reaction kettle is controlled 0.6.
Third walks, cooling, until when displays temperature is room temperature, collects the black product that inner liner of reaction kettle bottom obtains；It is right
Product absolute ethyl alcohol, deionized water are alternately washed, and are washed repeatedly repeatedly after centrifugation, are finally done product in vacuum
It is dried in vacuo in dry case；Obtained product is FeSn/rGO crystal seeds.
The FeSn/rGO crystal seeds of above-mentioned acquisition are dispersed in the ethanol solution of tin oxalate and ferric acetate, then by the 4th step
Ethylene glycol is added to above-mentioned solution；Magnetic agitation half an hour makes it be uniformly mixed, wherein the substance of tin oxalate and ferric acetate
The ratio between amount be 0.8:1, a concentration of 6mmol/L of ferric acetate, ferric acetate and the FeCl in the first step3·6H2The molar ratio of O is
0.3:1；Finally above-mentioned solution is transferred in the stainless steel cauldron of polytetrafluoroethyllining lining, then in an oven with per minute
0.5 DEG C of rate is heated to 170 DEG C, and is kept for 6 hours, and the charging coefficient of reaction kettle is controlled 0.6.
5th step, it is cooling, until when displays temperature is room temperature, collect the black product that inner liner of reaction kettle bottom obtains；It is right
Product absolute ethyl alcohol, deionized water are alternately washed, and are washed repeatedly repeatedly after centrifugation, are finally done product in vacuum
It is dried in vacuo in dry case；Obtained product is FeSn- nanometer stick arrays/rGO.
2) synthesis of tent type frame structure rGO/FeSn-NRsArray/rGO composite materials
FeSn- nanometer stick arrays/the rGO obtained in above-mentioned (3) is dispersed in scattered GO by the first step
(0.3mg/ml) aqueous solution, then by ethylene glycol and N2H4·H2O is added to above-mentioned solution, the GO and system that wherein the step is added
It is 1.2 to take the mass ratio for the GO being added when FeSn- nanometer stick arrays/rGO:1.
Second step, magnetic agitation half an hour make it be uniformly mixed.Finally above-mentioned solution is transferred in polytetrafluoroethylene (PTFE)
In the stainless steel cauldron of lining, the charging coefficient of reaction kettle is controlled 0.6, then in an oven with 0.5 DEG C of rate per minute
170 DEG C are heated to, and is kept for 6 hours.
Third walks, cooling, until when displays temperature is room temperature, collects the black product that inner liner of reaction kettle bottom obtains.It is right
Product absolute ethyl alcohol, deionized water are alternately washed, and are washed repeatedly repeatedly after centrifugation, are obtained tent type frame structure
Product is finally preserved and is dispersed in absolute ethyl alcohol by rGO/FeSn-NRsArray/rGO composite materials.
Embodiment 3
A kind of synthetic method of the graphene of tent type frame structure/FeSn- nanometer stick arrays/graphene composite material,
Include the following steps：
1) preparation of FeSn- nanometer stick arrays/rGO
The first step measures 2.5ml scattered GO (graphene oxide) (0.7mg/mL) aqueous solutions, polyethylene is added
Pyrrolidones (PVP) 0.315g, is then dispersed in triethylene glycol, and SnCl is added2·2H2O and FeCl3·6H2O is to above-mentioned molten
Liquid, magnetic agitation half an hour make it be uniformly mixed, wherein SnCl2·2H2O and FeCl3·6H2The molar ratio of O is 2.4:1,
The ratio of the dosage of graphene oxide and the dosage of inorganic molysite is 40g:1mol.
Then NaBH is added to mixed solution in second step4, addition and the first step be added graphene oxide addition it
Than for 0.5mol:Above-mentioned solution is finally transferred in the stainless steel cauldron of polytetrafluoroethyllining lining, then in an oven by 1g
190 DEG C are heated to 2 DEG C of speed per minute, and is kept for 4 hours, the charging coefficient of reaction kettle is controlled 0.79.
Third walks, cooling, until when displays temperature is room temperature, collects the black product that inner liner of reaction kettle bottom obtains；It is right
Product absolute ethyl alcohol, deionized water are alternately washed, and are washed repeatedly repeatedly after centrifugation, are finally done product in vacuum
It is dried in vacuo in dry case；Obtained product is FeSn/rGO crystal seeds.
The FeSn/rGO crystal seeds of above-mentioned acquisition are dispersed in the ethanol solution of tin oxalate and ferric acetate, then by the 4th step
Ethylene glycol is added to above-mentioned solution；Magnetic agitation half an hour makes it be uniformly mixed, wherein the substance of tin oxalate and ferric acetate
The ratio between amount be 1.2:1, a concentration of 4mmol/L of ferric acetate, ferric acetate and the FeCl in the first step3·6H2The molar ratio of O is
0.5:1；Finally above-mentioned solution is transferred in the stainless steel cauldron of polytetrafluoroethyllining lining, then in an oven with per minute
2 DEG C of rate is heated to 190 DEG C, and is kept for 4 hours, and the charging coefficient of reaction kettle is controlled 0.79.
5th step, it is cooling, until when displays temperature is room temperature, collect the black product that inner liner of reaction kettle bottom obtains；It is right
Product is alternately washed with anhydrous second, deionized water, is washed repeatedly repeatedly after centrifugation, is finally being dried in vacuo product
It is dried in vacuo in case；Obtained product is FeSn- nanometer stick arrays/rGO.
2) synthesis of tent type frame structure rGO/FeSn-NRsArray/rGO composite materials
FeSn- nanometer stick arrays/the rGO obtained in above-mentioned (3) is dispersed in scattered GO by the first step
(0.7mg/ml) aqueous solution, then by ethylene glycol and N2H4·H2O is added to above-mentioned solution, the GO and system that wherein the step is added
It is 0.8 to take the mass ratio for the GO being added when FeSn- nanometer stick arrays/rGO:1.
Second step, magnetic agitation half an hour make it be uniformly mixed.Finally above-mentioned solution is transferred in polytetrafluoroethylene (PTFE)
In the stainless steel cauldron of lining, the charging coefficient of reaction kettle is controlled 0.79, is then added in an oven with 2 DEG C of rate per minute
Heat is kept for 4 hours to 190 DEG C.
Third walks, cooling, until when displays temperature is room temperature, collects the black product that inner liner of reaction kettle bottom obtains.It is right
Product absolute ethyl alcohol, deionized water are alternately washed, and are washed repeatedly repeatedly after centrifugation, are obtained tent type frame structure
Product is finally preserved and is dispersed in absolute ethyl alcohol by rGO/FeSn-NRsArray/rGO composite materials.
This hair can be understood and applied the above description of the embodiments is intended to facilitate those skilled in the art
It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiment without having to go through creative labor.Therefore, the present invention is not limited to implementations here
Example, the modification made without departing from the scope of the invention all within protection scope of the present invention.
Claims (6)
1. a kind of synthetic method of graphene of tent type frame structure/FeSn- nanometer stick arrays/graphene composite material,
It is characterized in that, includes the following steps：
(1) synthesis of FeSn/ graphenes crystal seed
In organic solvent, and inorganic tin salt and inorganic molysite is added in graphene oxide and surfactant-dispersed by (1-1),
It is uniformly mixed；
Reducing agent is added in (1-2), is transferred in reaction kettle, is heated to 170~190 DEG C and keeps 4~6h, is subsequently cooled to room
Temperature obtains black solid product, is washed to the product and obtains FeSn/ graphene crystal seeds after being dried；
(2) synthesis of FeSn- nanometer stick arrays/graphene
Obtained FeSn/ graphene crystal seeds are dispersed in the organic solution of organic tin salt and organic molysite by (2-1), are added also
Originality organic solvent, is uniformly mixed；
(2-2) is transferred in reaction kettle, is heated to 170~190 DEG C and is kept 4~6h, then cools to room temperature, it is solid to obtain black
Body product washs the product and obtains FeSn- nanometer stick arrays/graphene after being dried；
(3) synthesis of graphene/FeSn- nanometer stick arrays/graphene composite material
(3-1) disperses obtained FeSn- nanometer stick arrays/graphene and graphene oxide in organic solvent, reduction to be added
Agent is uniformly mixed；
(3-2) is transferred in reaction kettle, is heated to 170~190 DEG C and is kept 4~6h, then cools to room temperature, it is solid to obtain black
Body product washs the product and obtains graphene/FeSn- nanometer stick arrays/stone of tent type frame structure after being dried
Black alkene composite material；
The molar ratio of inorganic tin salt and inorganic molysite is 1.6~2.4 in step (1-1):1, surfactant and graphite oxide
The mass ratio of alkene is 140~180:1, the dosage of graphene oxide and the ratio of inorganic molysite dosage are 25~40g:1mol；
In the organic solution of step (2-1), solvent is ethyl alcohol, a concentration of 4~6mmol/L of organic molysite, is had in organic solution
The molar ratio of machine tin salt and organic molysite is 0.8~1.2:1, the molar ratio of organic molysite and inorganic molysite in step (1-1)
It is 0.3~0.5:1；
The mass ratio of graphene oxide in step (3-1) and the graphene oxide in step (1-1) is 0.8~1.2:1；
The washing process alternately washs product absolute ethyl alcohol and deionized water repeatedly, passes through centrifugation point each time after washing
It will be separated by solid-liquid separation from method；
The heating rate of heating process in step (1-2) is 0.5~2 DEG C/min, the heating of the heating process in step (2-2)
Rate 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.
2. the graphene of tent type frame structure according to claim 1/FeSn- nanometer stick arrays/graphene composite wood
The synthetic method of material, which is characterized 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.
3. the graphene of tent type frame structure according to claim 1/FeSn- nanometer stick arrays/graphene composite wood
The synthetic method of material, which is characterized in that
Reducing agent in step (1-2) is NaBH4, NaBH4Addition and the ratio between the addition of graphene oxide in the step be
0.3~0.5mol:1g；
Reducing agent in step (3-1) is N2H4·H2O, N2H4·H2The addition of the addition of O and graphene oxide in the step
The ratio between amount is 0.15~0.2L:1g.
4. the graphene of tent type frame structure according to claim 1/FeSn- nanometer stick arrays/graphene composite wood
The synthetic method of material, which is characterized in that the inorganic tin salt is SnCl2·2H2O, the inorganic molysite are FeCl3·
6H2O。
5. the graphene of tent type frame structure according to claim 1/FeSn- nanometer stick arrays/graphene composite wood
The synthetic method of material, which is characterized in that organic tin salt is stannous oxalate, and organic molysite is ferric acetate.
6. the graphene of tent type frame structure according to claim 1/FeSn- nanometer stick arrays/graphene composite wood
The synthetic method of material, which is characterized in that the graphene oxide uses the aqueous solution of graphene oxide, graphene oxide to contain
Amount is 0.3~0.7mg/mL.
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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 |
|---|
| "Facile Synthesis of grapheme supported FeSn2 nanocrystals with enhanced Li-stroage capacity";Yaye et al.;《RSC Adv.》;20140430;第4卷;第17401-17404页,实验部分 * |
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