CN105609713A - Preparation method of SnO2/graphene aerogel nanocomposite material subjected to irradiation for lithium ion battery - Google Patents

Preparation method of SnO2/graphene aerogel nanocomposite material subjected to irradiation for lithium ion battery Download PDF

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CN105609713A
CN105609713A CN201510872371.3A CN201510872371A CN105609713A CN 105609713 A CN105609713 A CN 105609713A CN 201510872371 A CN201510872371 A CN 201510872371A CN 105609713 A CN105609713 A CN 105609713A
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sno
gas
irradiation
lithium ion
graphene
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CN105609713B (en
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陈志文
张乾
汪文峰
苗纯杰
胡志翔
任兰兰
陈大勇
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University of Shanghai for Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 relates to a preparation method of a SnO2/graphene aerogel nanocomposite material subjected to irradiation for a lithium ion battery, which is simple in operation, is moderate and controllable and is used for energy saving and environmental friendliness. The method mainly comprises the following steps of firstly, preparing spherical tin by oxidation-reduction reaction; secondly, carrying out a hydrothermal reaction of the tin spheres and graphene oxide; and finally preparing the SnO2/graphene aerogel nanocomposite material. When the SnO2/graphene aerogel nanocomposite material subjected to irradiation of different dosages is taken as a negative electrode of the lithium ion battery, the electrochemical performance is obviously improved compared with the nanocomposite material not subjected to irradiation after electrochemical test; such product has a relatively large specific surface area; and the product has potential application value in the field of a composite functional material, particularly in aspects of lithium ion battery energy storage, a sensor and the like.

Description

Lithium ion battery is used through irradiation SnO2The preparation method of/graphene aerogel nano composite material
Technical field
The present invention relates to a kind of tin ash/graphene aerogel nanometer through irradiation as lithium ion battery negative multipleThe preparation method of condensation material. Its method is that application oxidation-reduction method is prepared tin ball and improved Hummers legal system for graphite oxideAlkene, then utilizes hydro-thermal method by graphene oxide and the reaction of tin ball, thereby prepares tin ash/Graphene gas of function admirableGel nano composite material. The invention belongs to functional composite material field.
Background technology
Lithium ion battery is the main energy source of electronic equipment nowadays, because it has high stability and energy density, quiteBe subject to researcher's concern, be expected to become the capital equipment of following stored energy. Graphite is that current lithium ion battery is in commercial marketUse modal negative material, but its theoretical capacity only has 372mAhg-1, this far can not meet the demand in market. SinceAfter Fuji uses tin ash as lithium ion battery negative material, tin-based material has been subject to extensive concern. Tin ash isA kind of N-shaped semiconductor, the about 780mAhg of its theoretical capacity-1, being expected to substitute graphite becomes battery material of new generation. But, purePhase tin ash active material in charge and discharge process is easily pulverized, and causes in the decay of lithium ion deintercalation Process Energy obviously.
For addressing this problem, the pattern that changes tin ash is all paid close attention in great majority research, such as preparing tin ashNanometer sheet, nanometer rods, nanotube, hollow nanospheres, nanocube etc. These unique structures can subtract to a certain extentThe volumetric expansion of little lithium ion battery material in charge and discharge process, thus its circulating and reversible performance improved. But for long periodCirculation electric discharge or high power charging-discharging, this way often can not meet. Another kind of effectively mode is by titanium dioxideTin and conductive carbon based Material cladding. Graphene is considered to the potential carbon-based material of tool at present, and it has good electric chargeMobility, thermodynamics and chemical stability are good. Although have these advantages, easily there is group in Graphene in preparation processPoly-. For solving Graphene agglomeration traits, three-dimensional (3D) graphene aerogel just receives publicity.. Template, change are adopted at presentLearn vapour deposition process, electrochemical deposition method etc. and prepared spongy, foamed aeroge, this 3D graphene aerogel energyEnough effectively stop the reunion between graphene sheet layer, maintain higher specific area, thereby provide more for active materialAvtive spot. Xiao etc. have reported three-dimensional Fe2O3/ graphene aerogel has higher lithium ion memory property, Liu and Li etc.By compound to tin ash and graphene aerogel, prepare D S nO2/ graphene aerogel is also tested by gas sensing property, findsThis material is for NO2There is good sensitiveness.
Electronic beam irradiation technology aspect engineering and material modification is being one instrument effectively. Zheng etc. visit with electron beamStudied carefully the motion of golden nanometer particle in environment, Yutaro etc. have reported that employing electron beam irradiation method is at TiO2(110) upper growthSnO2. The discovery electron beam irradiations such as Sanjay can change the micro-structural of nano material, have good light in hydrolytic processCatalytic performance.
It is the key content of electrode material research for the research of tin ash and Graphene micro-structural. In this experiment,Use hydro-thermal method to probe into the preparation technology of tin ash/graphene aerogel, by changing graphene oxide concentration, adding saltThe modes such as acid are prepared tin ash/graphene aerogel ultra-thin, that be cross-linked with each other, and by electron beam irradiation, sample are carried outModification. Result shows: the composite after electron beam irradiation modified is compared with irradiation not, and chemical property has obtained significantlyImprove.
Summary of the invention
1, the object of this invention is to provide a kind of SnO through irradiation as lithium ion battery negative2/ graphene aerogelThe preparation method of nano composite material. The present invention uses through irradiation SnO as lithium ion battery2/ graphene aerogel is nano combinedThe preparation method of material, is characterized in that having following steps:
A. the potassium peroxydisulfate that is 1:1 by mass ratio and phosphorus pentoxide are dissolved in the appropriate concentrated sulfuric acid, are heated to 80 DEG C, then will3 grams of native graphites add above-mentioned solution, constant temperature 4 hours; Be cooled to room temperature, with after the deionized water dilution of 300 ~ 400 milliliters, quietPut 12 hours; Washing, suction filtration, dry in 60 DEG C of vacuum drying chambers;
B. the precursor obtaining is joined in the ice bath concentrated sulfuric acid of 120 milliliters, under agitation slowly add the KMnO of 15 grams4，In the process adding, maintain the temperature at 0 ~ 5 DEG C; Then temperature is controlled to 35 DEG C and is stirred to abundant reaction; Add 250 ~ 300 millisRise deionized water dilution, in dilution, also will in ice bath, make temperature lower than 5 DEG C; After stirring, add 700 ml deionized water,And add at once the H of 20 milliliter 30%2O2, mixture produces bubble, and color becomes glassy yellow;
C. leave standstill 12 hours, by said mixture suction filtration, and with the watery hydrochloric acid washing of the 1:10 of 1 liter, filter removal part metalsIon; Use again deionized water washing and filtering, remove unnecessary acid; By the dissolution of solid obtaining in water, the then ultrasonic solution that makesBe uniformly dispersed, obtain graphene oxide solution;
D. in addition, at room temperature, 0.8 gram of polyvinylpyrrolidone (PVP) is joined and fills 50 milliliters of diglycolsIn conical flask, stir 10 minutes, observe white powder and dissolve completely, it is colourless that solution is; Conical flask is placed in to oil bath pan, to temperatureDegree is elevated to 180 DEG C, adds 1.2 grams of SnCl2·2H2O, constant temperature 5-10 minute;
E. 0.8 gram of sodium borohydride is dissolved in 10 milliliters of diglycols, with after the Dispette rapid stirring several seconds, fastSpeed dropwise adds (approximately 30 droplets/minute of the diglycol solution rate of addition of sodium borohydride) in above-mentioned conical flask, maintainsTemperature is at 160-180 DEG C, and 10-25 minute, stops heating, is cooled to room temperature, uses ethanol centrifuge washing 3 times, and sample is placed in veryIn empty baking oven, 80 DEG C are dried, and obtain pure spherical tin simple substance;
F.0.15 gram spherical tin simple substance is dispersed in respectively in the graphene oxide of 45 milliliter of 2 mg/ml, adds 1.5 milliliters36.5wt% hydrochloric acid, fully stirs, and obtains colloidal sol, then the colloidal sol ultrasonic wave of gained is processed 3 hours, until formation blackGel; Sample is transferred in 100 milliliters of polytetrafluoroethylene (PTFE) reactors to 180 DEG C of constant temperature 8 hours; Question response still naturally cools toRoom temperature, by distilled water cyclic washing several for sample, obtains tin ash graphene aerogel. And identified as samples is designated asSnO2/GAs-0；
G. by SnO2/ GAs-0 is placed under the titanium window of a GJ-2-II electron accelerator with the accelerating potential of 2MeV and the electricity of 8mAStream, uses respectively dosage 140,280,560, and 840kGy carries out electron beam irradiation and (according to irradiation dose, distinguishes called after: SnO2/GAs-140,SnO2/GAs-280,SnO2/ GAs-560, and SnO2/ GAs-840); After all samples freeze drying 18 hoursMake lithium ion battery negative material.
2, lithium ion battery according to claim 1 is used through irradiation SnO2/ graphene aerogel nano composite materialPreparation method, it is characterized in that: in step f, can adopt equally 45 milliliters 3 and 5 mg/ml graphene oxide comePreparation SnO2/GAs-0。
3, lithium ion battery according to claim 1 is used through irradiation SnO2/ graphene aerogel nano composite materialPreparation method, it is characterized in that: in step a, the addition of potassium peroxydisulfate and phosphorus pentoxide is taking respectively as 2.5 grams forGood.
Brief description of the drawings
Fig. 1 is for to be respectively (a) 5mg/mL in GO concentration, and (b) 3mg/mL (c) prepares when 2mg/mLSnO2The scanning electron microscope (SEM) photograph of/GAs; And Fig. 1 (c) sample adds prepared SnO after hydrochloric acid2Basic, normal, high times of/GAs-0Scanning electron microscope (SEM) photograph (d)-(f).
Fig. 2 is SnO2The nitrogen desorption adsorption curve (a) of/GAs-0 sample and pore size distribution curve (b) figure.
Fig. 3 is SnO2Thermogravimetric analysis (TG) figure of/GAs-0 sample.
Fig. 4 is SnO2/GAs-0、SnO2/GAs-140、SnO2/GAs-280、SnO2/ GAs-560 and SnO2/ GAs-840 sampleThe X-ray diffractogram of product.
Fig. 5 is SnO2Transmission electron microscope (TEM) figure (a), (b) SnO of/GAs-0 sample2/GAs-0,(c)SnO2/GAs-140,(d)SnO2/GAs-280,(e)SnO2/ GAs-560 and (f) SnO2The high power transmission electron microscope of/GAs-840 sample(HRTEM) figure.
Fig. 6 is SnO2The charge-discharge performance (a) of/GAs-0 sample, SnO2/ GAs-0 and SnO2/GAs-140,280,560, and the discharge cycles of 840 samples (b), curve of double curvature (c), SnO2The charge-discharge performance (d) of/GAs-280 sampleFigure.
Fig. 7 is SnO2/GAs-0,SnO2/ GAs-280 and SnO2Fourier's infrared spectrum (FT-IR) of/GAs-840 sampleFigure.
Fig. 8 is SnO2/GAs-0,SnO2/ GAs-280 and SnO2The Raman collection of illustrative plates of/GAs-840 sample.
Detailed description of the invention
Now, by specific embodiments of the invention, be described further, be described below.
Embodiment
1. the potassium peroxydisulfate and the phosphorus pentoxide that quality are to 2.5g, be dissolved in the appropriate concentrated sulfuric acid, is heated to 80DEG C, then 3g native graphite is added to above-mentioned solution, constant temperature 4h; Be cooled to room temperature, rare by the deionized water of 300-400mlAfter releasing, leave standstill 12h; Washing, suction filtration, dry in 60 DEG C of vacuum drying chambers;
2. the precursor obtaining is joined in the ice bath concentrated sulfuric acid of 120ml, under agitation slowly add the KMnO of 15g4，In the process adding, maintain the temperature at 0 ~ 5 DEG C; Then temperature is controlled to 35 DEG C and is stirred to abundant reaction; Add 250 ~ 300The dilution of ml deionized water also will make temperature lower than 5 DEG C in ice bath in dilution; After stirring, add 700ml deionized water,And add at once the H of 20ml30%2O2, mixture produces bubble, and color becomes glassy yellow;
3. leave standstill 12h, by said mixture suction filtration, and with the watery hydrochloric acid washing of the 1:10 of 1L, filter removal part metals fromSon; Use again deionized water washing and filtering, remove unnecessary acid; By the dissolution of solid obtaining, in water, then the ultrasonic solution that makes dividesEvenly loose, obtain graphene oxide solution;
4. in addition, at room temperature, 0.8g polyvinylpyrrolidone (PVP) is joined and fills 50mL diglycolIn conical flask, stir 10 minutes, observe white powder and dissolve completely, it is colourless that solution is; Conical flask is placed in to oil bath pan, to temperatureDegree is elevated to 180 DEG C, adds 1.2gSnCl2·2H2O, constant temperature 5-10 minute;
5. 0.8g sodium borohydride is dissolved in 10mL diglycol, with after the Dispette rapid stirring several seconds, fastSpeed dropwise adds (approximately 30 droplets/minute of the diglycol solution rate of addition of sodium borohydride) in above-mentioned conical flask, maintainsTemperature is at 180 DEG C, and 15 minutes, stop heating, be cooled to room temperature, with ethanol centrifuge washing 3 times, sample is placed in to vacuum drying oven80 DEG C dry, obtains pure spherical tin simple substance;
6.0.15 gram spherical tin simple substance is dispersed in respectively in the graphene oxide of 45 milliliter of 2 mg/ml, adds 1.5 milliliters36.5wt% hydrochloric acid, fully stirs, and obtains colloidal sol, then the colloidal sol ultrasonic wave of gained is processed 3 hours, until formation blackGel; Sample is transferred in 100 milliliters of polytetrafluoroethylene (PTFE) reactors to 180 DEG C of constant temperature 8 hours; Question response still naturally cools toRoom temperature, by distilled water cyclic washing several for sample, obtains tin ash/graphene aerogel; And identified as samples is designated asSnO2/GAs-0；
7. by SnO2/ GAs-0 is placed under the titanium window of a GJ-2-II electron accelerator with the accelerating potential of 2MeV and 8mAElectric current, uses respectively dosage 140,280,560,840kGy carry out electron beam irradiation (according to irradiation dose, respectively called after:SnO2/GAs-140,SnO2/GAs-280,SnO2/ GAs-560 and SnO2/ GAs-840). After all samples freeze drying 18hMake lithium ion battery negative material.
About the method for testing of product electrode material of the present invention
Electrode enters with 8:1:1 according to active material (being tin ash/graphene aerogel), conductive agent (SuperP), adhesiveRow preparation, is placed in mortar by the active material of weighing and conductive agent and grinds 30 minutes, transfers in 5mL small beaker, adds stickyMixture, and drip 1-METHYLPYRROLIDONE 3-5 and drip, fully stir into slurry. Be 0.3mm by thickness, the copper that diameter is 14mmFor paper tinsel, acetone, ethanol reagent clean up, and weigh the quality of Copper Foil, drip 1-2 drip slurry with on Copper Foil with liquid-transfering gun, put intoIn 100-120 DEG C of vacuum drying chamber, more than dry 12h, take out pole piece, weigh the quality of pole piece. Weigh quality with every pole pieceBe multiplied by 0.80 quality as substantial activity material. Using the above-mentioned electrode slice of preparing as negative pole, using lithium metal as positive pole,Electrolyte is LiPF6Compound (wherein dimethyl carbonate (DMC): diethyl carbonate (DEC): the sub-second of carbonic acid with carbonatesEster (EC) is 1:1:1). All in the glove box lower than the ar gas environment of 1ppm, assemble CR2032 button electricity in moisture and oxygen contentPond, with circulation and the high rate performance of LAND2001A battery test system test battery, test process keeps 25 DEG C of constant temperature.
Instrument detects and characterizes
Now instrument detection and the characterization result of the present embodiment products therefrom are described below:
SEM detects (FESEM)
Use field emission scanning electron microscope (FESEM, model: JSM-6700F, manufacturer: company of NEC) forObserve the surface topography of sample. Shown in Fig. 1 (a-c) is the prepared SnO of GO of variable concentrations2/ graphene aerogel cutsThe scanning electron microscope (SEM) photograph of face, wherein in Fig. 1 (a), GO is 5mg/mL, and in Fig. 1 (b), GO is 3mg/mL, and in Fig. 1 (c), GO is 2Mg/mL, in the sample that Fig. 1 (d-f) is is 2mg/mL in GO concentration, adds 1.5mL36.5wt% hydrochloric acid and the SnO for preparing2/Basic, normal, high times of scanning electron microscope (SEM) photograph of graphene aerogel. In Fig. 1 (a), Graphene occurs stacking, does not form pore passage structure,This may be because GO concentration is compared with forming greatly stronger viscosity. Compared with Fig. 1 (a), in Fig. 1 (b), duct forms, but notLaunch pore size heterogeneity completely. Fig. 1 (c) can find out, now launch completely in duct, between graphene sheet layer, mutually hands overPitch stackedly, be loose structure, hole dimension is greatly between several microns to tens microns. See that from Fig. 1 (c) graphene sheet layer is not stillBe very thin, this explanation graphene sheet layer partly overlaps, and is not single-layer graphene film. When adding in 2mg/mL graphene oxideAfter 1.5mL36.5wt% hydrochloric acid, as shown in Fig. 1 (d-f), can find that graphene film is very thin, between lamella, be cross-linked with each other,Aperture is homogeneous comparatively, can be found out SnO by Fig. 1 (f)2Nano particle uniform load on graphene film, SnO2Granular size approximatelyBe 3 ~ 5nm. The structure of this uniqueness may cause due to the reason of following aspect: when the concentration of GO is too large, because viscosity increasesBy force, surface tension is larger, is unfavorable for Graphene layering; Simple substance tin and hydrochloric acid reaction have produced a large amount of hydrogen, the generation of gasAccelerate peeling off of graphene sheet layer; On graphene film, how much restrictions of tin ash particle can improve the contact at interfacePower, thereby the reunion of inhibition tin dioxide nano-particle.
Specific area and lacunarity analysis (BET)
Use specific area and lacunarity analysis instrument (BET, model: full-automatic 4 stations, manufacturer: Kang Ta instrument company of the U.S.)Analyze specific area and the porosity of gained powder sample. Shown in Fig. 2 (a) is SnO2The nitrogen adsorption desorption song of/GAs-0Line, belongs to IV type curve. At 0.43-1.0P/P0There is a H3 type hysteresis loop clearly in region, and this shows that sample has JiePore structure. Meanwhile, H3 type thermoisopleth is considered to relevant to the hole of platy particle or slit-shaped, for SnO2/ GAs-0,Slit between space and stannic oxide particle probably and between graphene sheet layer is relevant. Pore volume is 0.351cm3·g?1，Adsorbing its specific area of calculating by BJH is 364.04m2·g?1, this is than the employing SnCl reporting in document4Or SnCl2For frontTin ash/the graphene film that drives body and prepare is much higher. This has further confirmed that simple substance tin and hydrochloric acid reaction are conducive to stoneEffectively peeling off of China ink alkene lamella, thus the less tin ash/graphene aerogel of the number of plies formed. Larger specific area is favourableIn the chemical property that improves lithium ion battery, for lithium ion provides shorter transmission range and more living in transmitting procedureProperty site. Shown in Fig. 2 (b) is graph of pore diameter distribution, and the average pore size of sample is approximately 3 nanometers, and this may derive from graphene filmAnd gap between the nano particle of tin ash.
Thermogravimetric analysis (TG)
Use thermogravimetric analysis (model: STA409PC, TGA, German Netzsch company) to come heat endurance and the group of research materialPart. Fig. 3 is SnO2The thermogravimetric loss spectrogram of/GAs-0, as seen from the figure, the loss of 100 DEG C of left and right is mainly due to sampleIn moisture and the free evaporation of water of sample, be the pyrolysis due to Graphene the mass loss of 500-600 DEG C, by collection of illustrative platesCan calculate Graphene and account for dry SnO2The total proportion of/GAs-0 composite sample approximately 50.7%.
X ray diffraction analysis x (XRD)
Use and adopt X-ray diffractometer (instrument model: 18KWD/MAX2500V+/PC, manufacturer: Rigaku motor strainFormula commercial firm) gained powder sample is carried out to material phase analysis. Not tin ash/graphene aerogel sample of irradiation and irradiationAs shown in Figure 4, wherein highest peak is positioned at (110) crystal face diffraction maximum of 2 θ=26.6 ° to XRD, illustrates that (110) crystal face is titanium dioxideThe preferential growth face of tin, other diffraction maximum respectively in 2 θ=33.9,37.9,51.8 and 65.9 °, corresponding Tetragonal titanium dioxide(101), (200) of tin, (211) and (301) crystal faces (JCPDS41-1445), do not have the diffraction maximum of simple substance tin to occur, table in figureBright tin has been converted into tin ash completely. According to Scherer equation, calculated SnO from halfwidth2The average chi of particleVery little about 3.9nm, SnO2Nanocrystal disperses more even, and this is consistent with HRTEM result below. Can find out SnO simultaneously2/The crystallinity of GAs-0 is poor, SnO2/ GAs-280 diffraction maximum is stronger, and crystallinity is best, but along with irradiation dose further increases,There is not stronger diffraction maximum. The electron beam irradiation of this explanation doses, is conducive to improve the crystallinity of sample.
Transmission electron microscope detects (TEM)
Use a transmission electron microscope (TEM, model: JEM-2010F, manufacturer: company of NEC) to gainedPowder sample carries out microstructure analysis. That in Fig. 5 (a), show is SnO2The low power TEM image of/GAs-0, can find two in figureBe dispersed in to tin oxide nano uniform particles the aerocolloidal surface of Graphene, do not occur large area reunion, SnO2/GAs-0、140,280,560,840 HRTEM image is as shown in Fig. 5 (b) ~ (f). In Fig. 5 (b), can indistinctly see some lattice fringesPicture, the crystallinity of interpret sample a little less than, this and X-ray diffraction result match. Can find out titanium dioxide from Fig. 5 (c) with 5(d)The particle diameter of tin crystal approximately 3 ~ 5 nanometers. Lattice fringe picture is comparatively clear, and the crystallinity of Fig. 5 (d) is best. Can find out graphite simultaneouslyAlkene lamella is very thin, and tin oxide nano particles is evenly distributed on Graphene surface, does not have the region of Graphene all not occur dioxyChange tin particles, further confirm that Graphene, for stannic oxide particle growth provides avtive spot, has suppressed tin ash simultaneouslyThe reunion of grain. In the time that irradiation dose is increased to 840kGy, as shown in Fig. 5 (f), graphene film fold obviously strengthens, SnO2NanometerParticle aggregation, can find out that multiple-level stack has appearred in Graphene edge simultaneously, and this explanation irradiation dose is excessive, has destroyed GrapheneThe loose structure of aeroge, makes aeroge occur caving in, thereby causes that graphene sheet layer increases, and duct is blocked, and this may beCause one of factor of its chemical property reduction. , can be found out by Fig. 5 (d) illustration meanwhile, irradiation dose in the time of 280kGy,Occurred obvious lattice defect, these defects may come from oxygen vacancy, discomposition and stacking fault, and whether these defects canAffect the chemical property of nano material, be the problem that academia exists dispute always. As can be seen from the above analysis, too highIrradiation dose may cause the irradiation damage of sample, the irradiation of appropriateness can not cause damage to material, can improve on the contraryThe crystal property of tin ash, may produce more lattice defect simultaneously.
Chemical property detects
Use LANDCT2001A (the blue electric battery test system in Wuhan) to carry out chemical property survey to the button cell after sealingExamination. SnO2/ GAs-140, as shown in Figure 6, charging/discharging voltage is at 0.05-3.0 for the electric performance test of 280,560 and 840 samplesBetween V. Fig. 6 (a) is SnO2The cyclic curve of/GAs-0, as can be seen from the figure discharge capacity reaches 2060mAhg first-1，Charging capacity is 1094mAhg-1, coulombic efficiency approximately 53.11% first. Discharge capacity is down to 1133mAhg for the second time-1,This may be owing to forming Li2The cause that the inorganic solid electrolyte interlayer of O and electrolyte decompose. At the 10th circulation time, putCapacitance is reduced to about 700mAhg-1, capacity attenuation is obvious. Fig. 6 (b) is irradiation sample and the not electric discharge of irradiation sampleCycle performance, compared with irradiation sample not, irradiation sample has higher capacity and better cyclical stability, particularly greatlyThe approximately the 10th circulation is later obvious. Meanwhile, SnO2/ GAs-280 capacity is the highest, after 50 circulations, still can be stabilized in800mAh·g-1. Be not difficult to find out, irradiation dose is increased to 280kGy process from 0, and the capacity of battery increases, but irradiation doseFrom 280 to 840kGy processes, significantly increasing does not appear in capacity. The multiplying power circulation of irradiation sample and not irradiation sampleAs shown in Figure 6 (c), current density is from 0.1 to 1Ag-1. When current density is 0.1A.g-1, irradiation sample does not compare irradiationSample has higher capacity, is increased to 0.5Ag but work as current density-1And 1Ag-1Time, SnO2/ GAs-280 can divideDo not keep 750 and 450mAhg-1Specific capacity, this than before report relevant graphene-based tin ash composite willHigh. When current density is reduced to 0.1Ag-1Time, capacity is increased to 850mAhg-1. Meanwhile, Fig. 6 (d) shows SnO2/GAs-280 is 0.1Ag in current density-1Time demonstrate good stability in discharging and recharging. With SnO2/ GAs-0 compares, although itsFirst discharge specific capacity only has 1680mAhg-1, compare SnO2/ GAs-0 first discharge specific capacity is low, but its effect first coulombRate is higher, reaches 67.2%, and special capacity fade also wants much slow simultaneously, and discharge capacity is 1182mAhg for the second time-1,10After inferior circulation, Capacitance reserve is at 882mAhg-1, this will be far above SnO2/ GAs-0. So SnO2/ GAs-280 hasHigh reversible capacity. Above result shows, the SnO of irradiation2/ GAs sample has better chemical property, and irradiation doseWhen about 280kGy, chemical property is put up the best performance in irradiation sample.
Infrared spectrometer is analyzed
Use Fourier infrared spectrograph (model: Nicolet380, FTIR, manufacturer: Thermo Fischer Scient Inc.)Sample to preparation carries out complementary constituent analysis. Fig. 7 is SnO2/GAs-0,SnO2/ GAs-280 and SnO2/ GAs-840 sampleFourier's infared spectrum of product. At 3500cm-1And 1394cm-1Position is stretching vibration and the deformation vibration of corresponding hydroxyl respectively.For SnO2/ GAs-280 and SnO2/ GAs-840,1394cm-1Peak gradually a little less than, this may disappear with oxygen-containing functional groupAnd graphene oxide is further reduced relevant. 1646cm-1And 1515cm-1Peak is the flexural vibrations due to C=O and C=CCause. With SnO2/ GAs-0 compares, SnO2/ GAs-280,840 at 557cm-1And 615cm-1There is obvious suction in placeReceive peak, this with the Sn-O key of reporting in document form relevant, this peak obviously strengthen illustrate by after electron beam irradiation, titanium dioxideTin and Graphene have formed stronger interaction. SnO2/ GAs-280,840 at 3000-3700cm-1Peak a little less than, showAfter irradiation, hydroxyl is reduced, and intramolecular water content reduces. The above results shows, radiation treatment can be removed the energy containing oxygen officialGroup, the intensity of enhancing Sn-O key, these all may be relevant to its chemical property.
Raman spectrum analysis
Use Raman spectrum (model: STA409PC, Raman spectrometer Raman, thunder Renishaw company of Britain), excitation wavelength514.5nm, power is 3mW, sweep limits: 500-1800cm-1, for the qualification of material, the research of molecular structure. Fig. 8 isSnO2/GAs-0,SnO2/ GAs-280 and SnO2The Raman collection of illustrative plates of/GAs-840. At 1352cm-1And 1588cm-1Two peaksRespectively corresponding the sp of material with carbon element3Hydridization and sp2Hybrid characteristics vibration. 1352cm-1The degree of disorder of the corresponding material with carbon element of absworption peak(being defined as D peak), and at 1588cm-1Absworption peak correspondence the degree of graphitization (being defined as G peak) of material with carbon element. D peak be due toUnordered space oscillations of bringing out produces, and G peak is due to planar stretching vibration generation of material. Through conventional ID/IGCome anti-Answer the defect of material with carbon element, unordered degree and graphite hydridization degree. In Fig. 8, SnO2The I of/GAs-0 sampleD/IGBe about 1.10,SnO2The I of/GAs-840 sampleD/IGBe about 1.09, SnO2The I of/GAs-280 sampleD/IGBe about 1.06. Wherein SnO2/GAs-280 change obviously, and this variation shows after appropriate electron beam irradiation, sp2The region area of hydridization increases, but hydridization regionQuantity reduce. This may be because the hydroxyl of tin ash and Graphene, carboxyl, hydrone etc. be under electron beam irradiation condition,Produce the variation of stress, caused Graphene surface to produce that more atom defect causes. We think appropriate electronicsBundle irradiation, has produced large-area hydridization, and irradiation dose is excessive, may cause the atom damage of material. Therefore, Raman spectrumThe test result of test result and transmission electron microscope, infrared spectrum is consistent, has shown that appropriate electron beam irradiation can make material productionMore defect.

Claims (3)

1. use through irradiation SnO as lithium ion battery2The preparation method of/graphene aerogel nano composite material, is characterized in thatThere are following steps:
A. the potassium peroxydisulfate that is 1:1 by mass ratio and phosphorus pentoxide are dissolved in the appropriate concentrated sulfuric acid, are heated to 80 DEG C, then will3 grams of native graphites add above-mentioned solution, constant temperature 4 hours; Be cooled to room temperature, with after the deionized water dilution of 300 ~ 400 milliliters, quietPut 12 hours; Washing, suction filtration, dry in 60 DEG C of vacuum drying chambers;
B. the precursor obtaining is joined in the ice bath concentrated sulfuric acid of 120 milliliters, under agitation slowly add the KMnO of 15 grams4, addIn the process entering, maintain the temperature at 0 ~ 5 DEG C; Then temperature is controlled to 35 DEG C and is stirred to abundant reaction; Add 250 ~ 300 millilitersDeionized water dilution also will make temperature lower than 5 DEG C in ice bath in dilution; After stirring, add 700 ml deionized water, andAdd at once the H of 20 milliliter 30%2O2, mixture produces bubble, and color becomes glassy yellow;
C. leave standstill 12 hours, by said mixture suction filtration, and with the watery hydrochloric acid washing of the 1:10 of 1 liter, filter removal part metalsIon; Use again deionized water washing and filtering, remove unnecessary acid; By the dissolution of solid obtaining in water, the then ultrasonic solution that makesBe uniformly dispersed, obtain graphene oxide solution;
D. in addition, at room temperature, 0.8 gram of polyvinylpyrrolidone (PVP) is joined and fills 50 milliliters of diglycolsIn conical flask, stir 10 minutes, observe white powder and dissolve completely, it is colourless that solution is; Conical flask is placed in to oil bath pan, to temperatureDegree is elevated to 180 DEG C, adds 1.2 grams of SnCl2·2H2O, constant temperature 5-10 minute;
E. 0.8 gram of sodium borohydride is dissolved in 10 milliliters of diglycols, with after the Dispette rapid stirring several seconds, fastSpeed dropwise adds (approximately 30 droplets/minute of the diglycol solution rate of addition of sodium borohydride) in above-mentioned conical flask; MaintainTemperature is at 160-180 DEG C, and 10-25 minute, stops heating, is cooled to room temperature, uses ethanol centrifuge washing 3 times, and sample is placed in veryIn empty baking oven, 80 DEG C are dried, and obtain pure spherical tin simple substance;
F.0.15 gram spherical tin simple substance is dispersed in respectively in the graphene oxide of 45 milliliter of 2 mg/ml, adds 1.5 milliliters36.5wt% hydrochloric acid, fully stirs, and obtains colloidal sol, then the colloidal sol ultrasonic wave of gained is processed 3 hours, until formation blackGel; Sample is transferred in 100 milliliters of polytetrafluoroethylene (PTFE) reactors to 180 DEG C of constant temperature 8 hours; Question response still naturally cools toRoom temperature, by distilled water cyclic washing several for sample, obtains tin ash/graphene aerogel; And identified as samples is designated asSnO2/GAs-0；
G. by SnO2/ GAs-0 is placed under the titanium window of a GJ-2-II electron accelerator with the accelerating potential of 2MeV and the electricity of 8mAStream, uses respectively dosage 140,280,560, and 840kGy carries out electron beam irradiation and (according to irradiation dose, distinguishes called after: SnO2/GAs-140,SnO2/GAs-280,SnO2/ GAs-560, and SnO2/ GAs-840), all samples freeze drying is after 18 hoursMake lithium ion battery negative material.
2. lithium ion battery according to claim 1 is used through irradiation SnO2The preparation of/graphene aerogel nano composite materialMethod, is characterized in that: in step f, can adopt equally the graphene oxide of 3 and 5 mg/ml of 45 milliliters to prepareSnO2/GAs-0。
3. lithium ion battery according to claim 1 is used through irradiation SnO2The preparation of/graphene aerogel nano composite materialMethod, is characterized in that: in step a, the addition of potassium peroxydisulfate and phosphorus pentoxide is taking respectively as 2.5 grams as best.
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CN107857255A (en) * 2017-10-23 2018-03-30 上海大学 A kind of method that electron beam irradiation prepares porous graphene aeroge
CN109698326A (en) * 2017-10-23 2019-04-30 中国石油大学(华东) A kind of organic phosphorization tin/oxidized graphite composite material for sodium-ion battery cathode
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CN111762814A (en) * 2020-07-02 2020-10-13 西南大学 TiO2(B) Preparation and application of @ RGO aerogel negative electrode material
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