CN109742381A - A kind of SnO2/ graphene/PPy trielement composite material preparation method - Google Patents
A kind of SnO2/ graphene/PPy trielement composite material preparation method Download PDFInfo
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- CN109742381A CN109742381A CN201910149323.XA CN201910149323A CN109742381A CN 109742381 A CN109742381 A CN 109742381A CN 201910149323 A CN201910149323 A CN 201910149323A CN 109742381 A CN109742381 A CN 109742381A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of SnO2/ graphene/PPy trielement composite material preparation method, the composite material is by hydro-thermal-in-situ polymerization method in hollow SnO2PPy and graphene are wrapped up simultaneously in the surface of particle, utilize hollow SnO2With the PPy layers of synergy to buffer volumes variation, the two-dimensional graphene of introducing not only strengthens the intensity of electrode, while effectively increasing the migration rate of electronics and lithium ion in the electrodes, shows excellent cyclical stability and high rate performance, the SnO2/ graphene/PPy trielement composite material has structure novel, and preparation is simple, and raw material are cheap and easy to get, has huge industrial application value.
Description
Technical field
The invention discloses a kind of SnO2/ graphene/PPy trielement composite material preparation method, belongs to lithium ion battery
Negative electrode material technical field.
Background technique
SnO2Material has higher theoretical specific capacity (782mAhg-1), much higher than the graphite electrode theory specific volume of commercialization
Measure (372mAhg-1), simultaneously because it has the excellent characteristics such as low cost, high security and nontoxicity, it is considered to be most latent
The next-generation lithium ion battery negative material of power, but material SnO in charge and discharge process2Huge volume can occur for particle
Variation, quickly decays so as to cause capacity, significantly limits its application range.To solve the above-mentioned problems, SnO is improved2
The cyclical stability of negative electrode material shortens the diffusion path of lithium, reduces its volume change bring internal stress, and preparation has specific
The nano SnO of structure2Particle, such as SnO2Nanometer stick array, nanotube, hollow nanostructures or in SnO2Draw in negative electrode material
Enter conducting polymer, can buffer the huge volume change of solia particle while improving conductivity of composite material and generate
Internal stress.Currently, SnO2/ PPy binary composite, such as SnO2/ PPy core-shell structure, SnO2It is/PPy mixing nano wire, hollow
SnO2/ PPy nanocomposite, with individual SnO2Particle is compared, SnO2The cycle performance of/PPy binary complex has greatly
It is promoted, polymer substrate effectively prevents SnO2The aggregation of nanoparticle has buffered huge volume change bring capacity
Attenuation problem.
Carbon material modifies SnO as buffer layer2When compound, since it has good electric conductivity and slows down internal stress
Ability, the cyclical stability of electrode can be improved.The one kind of graphene as carbon material, has the following advantages that, such as: excellent is soft
Toughness, big specific surface area (2630m2·g-1), chemical stability, good electric conductivity and thermal conductivity, therefore in fuel cell
Catalyst field and sensitizing dyestuff area of solar cell all attract attention.In addition, leading in battery and supercapacitor field
The storage and diffusivity of ion and electronics can be improved in the graphene for crossing chemical method functionalization.But single graphene
Cathode is more than 50% irreversible capacity loss since lamella accumulation problem shows it just in short-term charge and discharge cycles,
Therefore, solid particles need to be introduced in graphene layer, mitigates the accumulation problem of graphene.Although by introduce conducting polymer or
Graphene constructs SnO2Negative electrode material binary complex system, but how SnO is further increased on the basis of original2Cathode
Chemical property still have greatly improved space.
Summary of the invention
Goal of the invention: the poor, preparation method for existing lithium ion battery negative material cycle performance and high rate performance
The problems such as complex, efficiency is lower and higher cost, the invention discloses a kind of SnO2/ graphene/PPy tri compound material
The preparation method of material.
A kind of technical solution: SnO2/ graphene/PPy trielement composite material preparation method, comprising the following steps:
1, oxidation-reduction method synthesizing graphite alkene material is utilized；
2, by Na2SnO3·3H2O is dissolved in solvent, obtains SnO after hydro-thermal, centrifugation, drying, heat treatment2Hollow microsphere；
3, the deionized water solution containing surfactant and graphene is added to the SnO as made from step 22It is hollow
In microballoon, conducting polymer monomer and oxidant are added after being sufficiently mixed, and product centrifugation, washing, the drying of generation obtain
SnO2/ graphene/PPy trielement composite material.
Wherein, in step 2, hydro-thermal method synthesizes hollow SnO2The hydrothermal temperature of material be 160~200 DEG C, the time be 24~
30h；Hydro-thermal method synthesizes hollow SnO2The prepared Na of material2SnO3·3H2The concentration of O solution is 10~15mmolL-1, solvent
For the mixed solution of ethyl alcohol and deionized water.
In step 3, surfactant that the in-situ polymerization stage uses for lauryl sodium sulfate, dodecyl sodium sulfate,
The one or more of neopelex；The conducting polymer monomer that the in-situ polymerization stage uses is pyrroles, aniline, thiophene
One kind；The oxidant that the in-situ polymerization stage uses is ammonium persulfate solution；Each material quality ratio SnO2: graphene: PPy 60
~80%:10~30%:10~20%.
The utility model has the advantages that compared with the prior art, the present invention has the advantages that SnO2/ graphene/PPy trielement composite material
Synthesis technology it is easy, quick, at low cost, significantly shorten the development cycle of material, be conducive to industrial application.It prepares simultaneously
SnO2/ graphene/PPy trielement composite material integrates high conductivity, high capacity, excellently buffer volumes changing capability,
An important technological approaches, hollow SnO are given efficiently to prepare novel cathode material for lithium ion battery2It is solved with PPy layers
The huge volume change that material occurs in charge and discharge process, the two-dimensional graphene of introducing not only strengthen the strong of electrode
Degree, effectively improves the efficiency of transmission of electronics and lithium ion in the electrodes, shows excellent cyclical stability and forthright again
Energy.
Detailed description of the invention
Fig. 1 is the X-ray diffractogram of trielement composite material prepared by the present invention；
Fig. 2 is the scanning electron microscope (SEM) photograph of trielement composite material prepared by the present invention；
Fig. 3 is the transmission electron microscope picture of trielement composite material prepared by the present invention；
Fig. 4 is charge-discharge performance curve graph of the trielement composite material prepared by the present invention under 0.1C current density.
Specific embodiment
Invention is further described in detail with reference to the accompanying drawings and examples.
Embodiment 1:
Step 1, with oxidation-reduction method synthesizing graphite alkene material.In the 250mL three-necked bottle equipped with mechanical agitator, it is added
The 150mL concentrated sulfuric acid, ice bath are cooled to 0 DEG C.Into the above concentrated sulfuric acid, 6.5g graphite powder is added.Under stiring, into three-necked bottle,
19.5g KMnO is added portionwise4, reaction temperature is no more than 20 DEG C.KMnO4After addition, continue to stir 40min under ice bath.
Then, the reaction was continued at 35 DEG C 2h, then above-mentioned reaction solution is poured into the distilled water of 460mL, continue to stir at 60 DEG C
1h.Then, reaction solution is poured into the mixed solution of 1.4L water and 100mL hydrogen peroxide, stirring is for 24 hours.Filtering, it is molten with 5% hydrochloric acid
Liquid washs three times, and 70 DEG C of drying 72h obtain graphite oxide.By graphite oxide at 800 DEG C, after being sintered 60s, graphene is obtained；
Step 2, hydro-thermal method synthesize hollow SnO2Material.Prepare 15mmolL-1Na2SnO3·3H2O deionized water/nothing
Hydrous ethanol solution (volume ratio 5:3), addition urea make its concentration reach 0.1molL-1, solution is moved into polytetrafluoroethyllining lining
Stainless steel water heating kettle in, for 24 hours, natural cooling, obtained precipitating is through deionized water for 180 DEG C of hydro-thermals in Constant Temp. Oven
For several times with dehydrated alcohol washing centrifugation, it is dried in 70 DEG C, then 500 DEG C of heat treatments 1h, obtained SnO in tube furnace2It is hollow
Microballoon；
Step 3, situ aggregation method synthesizing new SnO2/ graphene/PPy trielement composite material.The hollow SnO of 0.1g2Microballoon is mixed
It closes in the deionized water solution for containing 4mg neopelex (SDS) and 0.02g graphene into 40mL, ultrasonic 30min,
Then magnetic agitation 3h.Inject 25.8 μ LPy monomers in the above solution later, then persistently after stirring 1h, concentration is added dropwise dropwise is
0.1·mol L-1Ammonium persulfate solution 11.18mL, persistently 4h uses the black object centrifugal treating of generation under stirring at room temperature
Deionized water and alcohol at least wash 3 times, then dry under 80 DEG C of vacuum drying temperature, obtain final sample.
Embodiment 2:
Step 1, with oxidation-reduction method synthesizing graphite alkene material the step of, are identical as the step 1 in embodiment 1；
Step 2, hydro-thermal method synthesize hollow SnO2Material.Prepare 15mmolL-1Na2SnO3·3H2O deionized water/nothing
Hydrous ethanol solution (volume ratio 5:3), addition urea make its concentration reach 0.1molL-1, solution is moved into polytetrafluoroethyllining lining
Stainless steel water heating kettle in, 160 DEG C of hydro-thermal 30h, natural cooling in Constant Temp. Oven, obtained precipitating is through deionized water
For several times with dehydrated alcohol washing centrifugation, it is dried in 70 DEG C, then 500 DEG C of heat treatments 1h, obtained SnO in tube furnace2It is hollow
Microballoon；
Step 3, situ aggregation method synthesizing new SnO2/ graphene/PPy trielement composite material.The hollow SnO of 0.1g2Microballoon is mixed
It closes in the deionized water solution for containing 4mg lauryl sodium sulfate and 0.025g graphene into 40mL, ultrasonic 30min, then magnetic
Power stirs 3h.Inject 25.8 μ LPy monomers in the above solution later, then persistently after stirring 1h, it is 0.1 that concentration is added dropwise dropwise
mol L-1Ammonium persulfate solution 11.18mL, under stirring at room temperature lasting 4h, by the black object centrifugal treating of generation, spend from
Sub- water and alcohol at least wash 3 times, then dry under 80 DEG C of vacuum drying temperature, obtain final sample.
Embodiment 3:
Step 1, with oxidation-reduction method synthesizing graphite alkene material the step of, are identical as the step 1 in embodiment 1；
Step 2, hydro-thermal method synthesize hollow SnO2Material.Prepare 10mmolL-1Na2SnO3·3H2O deionized water/nothing
Hydrous ethanol solution (volume ratio 5:3), addition urea make its concentration 0.1molL-1, solution is moved into polytetrafluoroethyllining lining
In stainless steel water heating kettle, in Constant Temp. Oven 200 DEG C of hydro-thermals for 24 hours, natural cooling, obtained precipitating through deionized water and
Dehydrated alcohol washing centrifugation for several times, is dried, then 500 DEG C of heat treatments 1h, obtained SnO in tube furnace in 70 DEG C2It is hollow micro-
Ball；
Step 3, situ aggregation method synthesizing new SnO2/ graphene/PPy trielement composite material.The hollow SnO of 0.1g2Microballoon is mixed
It closes in the deionized water solution for containing 4mg dodecyl sodium sulfate and 0.01g graphene into 40mL, ultrasonic 30min, then magnetic force
Stir 3h.Inject 25.8 μ LPy monomers in the above solution later, then persistently after stirring 1h, it is 0.1mol that concentration is added dropwise dropwise
L-1Ammonium persulfate solution 11.18mL, persistently the black object centrifugal treating of generation is used deionized water by 4h under stirring at room temperature
It is at least washed 3 times with alcohol, it is then dry under 80 DEG C of vacuum drying temperature, obtain final sample.
Fig. 1 is the SnO of embodiment 1 provided by the invention preparation2/ graphene/PPy trielement composite material X-ray diffraction
Scheme, as can be seen from the figure SnO2/ graphene/PPy diffraction maximum all well corresponding cubic phase rutile type SnO2
The characteristic peak of (cassiterite, JCPDS no.41-1445), there is no apparent rGO and PPy characteristic peaks.This is because phase
Than in SnO2, the diffraction peak intensity of graphene wants weak more, and the content of graphene and PPy in the composite is relatively low, meanwhile,
(002) crystal face and SnO of rGO2(110) crystal face be overlapped to a certain extent.In addition, since PPy itself is non crystalline structure, and
Characteristic peak is not shown, so trielement composite material only shows SnO2Characteristic peak.
Fig. 2 is the SnO of embodiment 1 provided by the invention preparation2/ graphene/PPy trielement composite material scanning electron microscope
Figure, it can be seen that having SnO in the outside of nonwoven fabric from filaments from scanning electron microscope (SEM) photograph2Microballoon adherency, while also some SnO2Microballoon quilt
Nonwoven fabric from filaments cladding, SnO2Microballoon and nonwoven fabric from filaments weave in form tridimensional network, the SnO of the method preparation2Particle compared with
It is uniformly dispersed in graphene/PPy.
Fig. 3 is the SnO of embodiment 1 provided by the invention preparation2/ graphene/PPy trielement composite material transmission electron microscope
Figure, it can be seen that some scattered SnO from transmission electron microscope picture2It is particle studded in graphene and PPy, the lattice of 0.335nm
Spacing can be determined as SnO2(110) crystal face of nano particle, the rGO in figure is presented multi-layer graphene piece and stacks, between lattice
Away from about 0.36nm, greater than the spacing of lattice of the 0.335nm of pure graphite, this illustrates that oxygen-containing group remaining on rGO increases stone
The interlamellar spacing of ink sheet, in graphene and SnO2It can be seen that amorphous PPy coating outside particle.
Fig. 4 is the SnO of embodiment 1 provided by the invention preparation2/ graphene/PPy trielement composite material is close in 0.1C electric current
Charge-discharge performance curve graph under degree, as seen from Figure 4, novel SnO2/ graphene/PPy trielement composite material exists
Under the charging and discharging currents of 0.1C, after stablizing 100 circle of circulation, reversible discharge capacity still can reach 647.8mAhg-1, have good
Invertibity and cyclical stability.
Claims (8)
1. a kind of SnO2/ graphene/PPy trielement composite material preparation method, which comprises the following steps:
(1) oxidation-reduction method synthesizing graphite alkene material is utilized；
(2) by Na2SnO3·3H2O is dissolved in solvent, obtains SnO after hydro-thermal, centrifugation, drying, heat treatment2Hollow microsphere；
(3) deionized water solution containing surfactant and graphene is added to the SnO as made from step (2)2Hollow microsphere
In, conducting polymer monomer and oxidant are added after being sufficiently mixed, and product centrifugation, washing, the drying of generation obtain
SnO2/ graphene/PPy trielement composite material.
2. a kind of SnO according to claim 12/ graphene/PPy trielement composite material preparation method, which is characterized in that
Na in the step (2)2SnO3·3H2The concentration of O solution is 10~15mmolL-1。
3. a kind of SnO according to claim 12/ graphene/PPy trielement composite material preparation method, which is characterized in that
Solvent in the step (2) is the mixed solution of ethyl alcohol and deionized water.
4. a kind of SnO according to claim 12/ graphene/PPy trielement composite material preparation method, which is characterized in that
Hydrothermal temperature in the step (2) is 160~200 DEG C, and the time is 24~30h.
5. a kind of SnO according to claim 12/ graphene/PPy trielement composite material preparation method, which is characterized in that
Surfactant in the step (3) be lauryl sodium sulfate, dodecyl sodium sulfate, neopelex one
Kind is several.
6. a kind of SnO according to claim 12/ graphene/PPy trielement composite material preparation method, which is characterized in that
Conducting polymer monomer in the step (3) is one kind of pyrroles, aniline, thiophene.
7. a kind of SnO according to claim 12/ graphene/PPy trielement composite material preparation method, which is characterized in that
Oxidant in the step (3) is ammonium persulfate solution.
8. a kind of SnO according to claim 12/ graphene/PPy trielement composite material preparation method, which is characterized in that
SnO in the step (3)2: graphene: the mass ratio of PPy is 60~80%:10~30%:10~20%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110212191A (en) * | 2019-06-25 | 2019-09-06 | 黑龙江省科学院高技术研究院 | A kind of graphene/SnO2The preparation method of/Si@PPy composite material |
| CN111892080A (en) * | 2020-08-07 | 2020-11-06 | 河南大学 | Preparation method of graphene and tin oxide hollow sphere composite nanomaterial |
| CN113793914A (en) * | 2021-09-10 | 2021-12-14 | 陕西科技大学 | Reduced graphene oxide coated CNTs/SnO with hollow structure2Composite film and preparation method and application thereof |
| CN114975964A (en) * | 2022-06-28 | 2022-08-30 | 四川轻化工大学 | Polypyrrole-coated tin dioxide/nano carbon sphere negative electrode material, preparation method thereof and sodium ion battery |
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| CN106531468A (en) * | 2016-11-24 | 2017-03-22 | 桂林理工大学 | Preparation method for sulfonated graphene oxide/stannic dioxide/polypyrrole composite material |
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| CN106531468A (en) * | 2016-11-24 | 2017-03-22 | 桂林理工大学 | Preparation method for sulfonated graphene oxide/stannic dioxide/polypyrrole composite material |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110212191A (en) * | 2019-06-25 | 2019-09-06 | 黑龙江省科学院高技术研究院 | A kind of graphene/SnO2The preparation method of/Si@PPy composite material |
| CN110212191B (en) * | 2019-06-25 | 2021-12-14 | 黑龙江省科学院高技术研究院 | graphene/SnO2Preparation method of/Si @ PPy composite material |
| CN111892080A (en) * | 2020-08-07 | 2020-11-06 | 河南大学 | Preparation method of graphene and tin oxide hollow sphere composite nanomaterial |
| CN111892080B (en) * | 2020-08-07 | 2022-03-29 | 河南大学 | Preparation method of graphene and tin oxide hollow sphere composite nanomaterial |
| CN113793914A (en) * | 2021-09-10 | 2021-12-14 | 陕西科技大学 | Reduced graphene oxide coated CNTs/SnO with hollow structure2Composite film and preparation method and application thereof |
| CN113793914B (en) * | 2021-09-10 | 2023-02-14 | 陕西科技大学 | Reduced graphene oxide coated CNTs/SnO with hollow structure 2 Composite film and preparation method and application thereof |
| CN114975964A (en) * | 2022-06-28 | 2022-08-30 | 四川轻化工大学 | Polypyrrole-coated tin dioxide/nano carbon sphere negative electrode material, preparation method thereof and sodium ion battery |
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Application publication date: 20190510 |