CN105609713B - The irradiated SnO of lithium ion battery2The preparation method of/graphene aerogel nano composite material - Google Patents
The irradiated SnO of lithium ion battery2The preparation method of/graphene aerogel nano composite material Download PDFInfo
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Abstract
The present invention relates to a kind of simple to operate, the preparation method of gentle controllable, energy-conserving and environment-protective irradiation tin ash/graphene aerogel nano composite material, belong to composite functional material field.The inventive method is to the effect that：Spherical tin is prepared using redox reaction, then tin ball and graphene oxide are subjected to hydro-thermal reaction, finally prepares tin ash/graphene aerogel nano composite material.By the irradiated tin ash of various dose/graphene aerogel nano composite material, as negative electrode of lithium ion battery, by electro-chemical test, compared to non-irradiated nano composite material, chemical property is significantly improved.This product has the high specific surface area of comparison.Product of the present invention has potential application value in composite functional material field especially lithium ion battery energy storage, sensor etc..
Description
Technical field
The present invention relates to a kind of irradiated tin ash/graphene aerogel nanometer as negative electrode of lithium ion battery to answer
The preparation method of condensation material.Its method is to prepare tin ball using oxidation-reduction method and improved Hummers methods prepare graphite oxide
Alkene, then graphene oxide and tin ball are reacted using hydro-thermal method, so as to prepare the tin ash of function admirable/graphene gas
Gel nanocomposites.The invention belongs to functional composite material field.
Background technology
Lithium ion battery is nowadays electronic equipment main energy sources, because it has high stability and energy density, quite
Paid close attention to by researcher, be expected to turn into the capital equipment of future energy storage.Graphite is current lithium ion battery in commercial market
Using most common negative material, but its theoretical capacity only has 372 mAhg-1, this is far from meeting the needs of market.Since
After Fuji uses tin ash as lithium ion battery negative material, tin-based material receives extensive concern.Tin ash is
It is a kind ofnType semiconductor, the mAhg of its theoretical capacity about 780-1, being expected to replacement graphite turns into battery material of new generation.It is but pure
Phase tin ash active material in charge and discharge process easily crushes, and causes obvious in the decay of lithium ion deintercalation Process Energy.
To solve this problem, most of researchs all focus on changing the pattern of tin ash, for example prepare tin ash
Nanometer sheet, nanometer rods, nanotube, hollow nanospheres, nanocube etc..These unique structures can subtract to a certain extent
Volumetric expansion of the small lithium ion battery material in charge and discharge process, so as to improve its circulating and reversible performance.But for long period
Circulation electric discharge or high power charging-discharging for, this method tends not to meet.Another effective manner is by titanium dioxide
Tin is compound with conducting carbon-based material.Graphene is considered as current most potential carbon-based material, and it has preferable electric charge
Mobility, thermodynamics and chemical stability are good.Although having these advantages, group easily occurs in preparation process for graphene
It is poly-.To solve graphene agglomeration traits, three-dimensional (3D) graphene aerogel just attracts attention.At present using template, change
Learn vapour deposition process, electrochemical deposition method etc. and prepare spongy, foam-like aeroge, this 3D graphene aerogels energy
Enough reunions effectively prevented between graphene sheet layer, maintain higher specific surface area, so as to be provided more for active material
Avtive spot.Xiao etc. reports three-dimensional Fe2O3/ graphene aerogel possesses higher lithium ion storage performance, Liu and Li etc.
Tin ash is compound with graphene aerogel, it is prepared for D S nO2/ graphene aerogel is simultaneously tested by gas sensing property, is found
The material is for NO2With good sensitiveness.
Electronic beam irradiation technology is a kind of effectively instrument in terms of engineering and material modification.Zheng etc. is visited with electron beam
The motion of golden nanometer particle in environment is studied carefully, Yutaro etc. is reported using electron beam irradiation method in TiO2(110) grown on
SnO2.Sanjay etc. has found that electron beam irradiation can change the micro-structural of nano material, has good light in hydrolytic process
Catalytic performance.
Research for tin ash and graphene micro-structural is the key content of electrode material research.In this experiment,
The preparation technology of tin ash/graphene aerogel is probed into using hydro-thermal method, by changing graphene oxide concentration, addition salt
The modes such as acid prepare tin ash/graphene aerogel that is ultra-thin, being cross-linked with each other, and sample is carried out by electron beam irradiation
It is modified.As a result show：Compared with non-irradiated, chemical property has obtained significantly composite after electron beam irradiation modified
Improve.
The content of the invention
1st, it is an object of the invention to provide a kind of irradiated SnO as negative electrode of lithium ion battery2/ graphene aerogel
The preparation method of nano composite material.The present invention is used as the irradiated SnO of lithium ion battery2/ graphene aerogel is nano combined
The preparation method of material, it is characterised in that have steps of：
A. it is 1 by mass ratio:1 potassium peroxydisulfate and phosphorus pentoxide is dissolved in the appropriate concentrated sulfuric acid, is heated to 80 DEG C, so
3 grams of native graphites are added into above-mentioned solution, constant temperature 4 hours afterwards；Room temperature is cooled to, is diluted with 300 ~ 400 milliliters of deionized waters
Afterwards, 12 hours are stood；Washing, filter, dried in 60 DEG C of vacuum drying chambers；
B. obtained precursor is added in 120 milliliters of the ice bath concentrated sulfuric acid, is slowly added into 15 grams under agitation
KMnO4, 0 ~ 5 DEG C is maintained the temperature at during addition；Then by temperature control in 35 DEG C of stirrings to abundant reaction；Addition 250 ~
300 ml deionized waters dilute, and temperature is less than 5 DEG C in dilution in ice bath；After stirring add 700 milliliters go from
Sub- water, and it is added immediately 20 milliliter 30% of H2O2, mixture produces bubble, and color becomes glassy yellow；
C. 12 hours are stood, said mixture is filtered, and with the 1 of 1 liter:10 watery hydrochloric acid washing, is filtered off except part
Metal ion；Filtering is washed with deionized again, removes unnecessary acid；By obtained solid dissolving in water, then ultrasound makes
Solution is uniformly dispersed, and obtains graphene oxide solution；
D. in addition, at room temperature, 0.8 gram of polyvinylpyrrolidone (PVP) being added to and fills 50 milliliter of one contracting diethyl two
In the conical flask of alcohol, stir 10 minutes, observation white powder is completely dissolved, and solution is in colourless；Conical flask is placed in oil bath pan,
180 DEG C are increased to temperature, adds 1.2 grams of SnCl2·2H2O, constant temperature 5-10 minutes；
E. 0.8 gram of sodium borohydride is dissolved in 10 milliliters of diglycols, the several seconds is quickly stirred with Dispette
Afterwards, quickly it is added dropwise in above-mentioned conical flask（Diglycol solution rate of addition about 30 drops/minute of sodium borohydride）,
Maintain temperature 10-25 minutes, to stop heating, be cooled to room temperature at 160-180 DEG C, with ethanol centrifuge washing 3 times, sample is put
80 DEG C of dryings in vacuum drying oven, obtain pure spherical tin simple substance；
F.0.15 gram spherical tin simple substance is dispersed in the graphene oxide of 45 milliliter of 2 mg/ml respectively, adds 1.5 millis
36.5wt% hydrochloric acid is risen, is sufficiently stirred, obtains colloidal sol, then by the colloidal sol ultrasonication 3 hours of gained, until forming black
Gel；Transfer the sample into 100 milliliters of ptfe autoclaves, 180 DEG C of constant temperature 8 hours；Question response kettle natural cooling
To room temperature, sample is washed for several times repeatedly with distilled water, that is, obtains tin ash graphene aerogel.And sample is labeled as
SnO2/GAs-0；
G. by SnO2/ GAs-0 is placed under the titanium window of an electron accelerator of GJ-2- II with 2MeV accelerating potential and 8mA
Electric current, respectively with the kGy of dosage 140,280,560,840 carry out electron beam irradiation（According to irradiation dose, it is respectively designated as：
SnO2/GAs-140, SnO2/GAs-280, SnO2/ GAs-560, and SnO2/GAs-840）；All samples freeze-drying 18 is small
When after be made lithium ion battery negative material.
2nd, the irradiated SnO of lithium ion battery according to claim 12/ graphene aerogel nano composite material
Preparation method, it is characterised in that：In step f, equally can using the graphene oxide of 45 milliliters of 3 and 5 mg/mls come
Prepare SnO2/GAs-0。
3rd, the irradiated SnO of lithium ion battery according to claim 12/ graphene aerogel nano composite material
Preparation method, it is characterised in that：In step a, the addition of potassium peroxydisulfate and phosphorus pentoxide is to be respectively 2.5 grams for most
It is good.
Brief description of the drawings
Fig. 1 is to be prepared in GO concentration respectively (a) 5 mg/mL, (b) 3 mg/mL, (c) 2 mg/mL
SnO2/ GAs scanning electron microscope (SEM) photograph；And the SnO prepared by after Fig. 1 (c) samples addition hydrochloric acid2Basic, normal, high times of/GAs-0
Scanning electron microscope (SEM) photograph (d)-(f).
Fig. 2 is SnO2The nitrogen desorption adsorption curve of/GAs-0 samples（a）And pore size distribution curve（b）Figure.
Fig. 3 is SnO2The thermogravimetric analysis of/GAs-0 samples（TG）Figure.
Fig. 4 is SnO2/GAs-0、SnO2/GAs-140、SnO2/GAs-280、SnO2/ GAs-560 and SnO2/ GAs-840 samples
The X-ray diffractogram of product.
Fig. 5 is SnO2The transmission electron microscope of/GAs-0 samples（TEM）Figure（a）, (b) SnO2/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 samples
（HRTEM）Figure.
Fig. 6 is SnO2The charge-discharge performance of/GAs-0 samples（a）, 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 of/GAs-280 samples（d）
Figure.
Fig. 7 is SnO2/GAs-0, SnO2/ GAs-280 and SnO2The FTIR spectrum of/GAs-840 samples（FT-IR）
Figure.
Fig. 8 is SnO2/GAs-0, SnO2/ GAs-280 and SnO2The Raman collection of illustrative plates of/GAs-840 samples.
Embodiment
Now by the specific embodiment of the present invention, it is described further, is described below.
Embodiment
1. being 2.5 g potassium peroxydisulfate and phosphorus pentoxide by quality, it is dissolved in the appropriate concentrated sulfuric acid, is heated to 80
DEG C, 3 g native graphites are then added into above-mentioned solution, the h of constant temperature 4；Room temperature is cooled to, the deionized water with 300-400 ml is dilute
After releasing, 12 h are stood；Washing, filter, dried in 60 DEG C of vacuum drying chambers；
2. obtained precursor is added in the 120 ml ice bath concentrated sulfuric acid, it is slowly added into 15 g's under agitation
KMnO4, 0 ~ 5 DEG C is maintained the temperature at during addition；Then by temperature control in 35 DEG C of stirrings to abundant reaction；Add
250 ~ 300 ml deionized waters dilute, and temperature is less than 5 DEG C in dilution in ice bath；700 ml are added after stirring to go
Ionized water, and it is added immediately the % of 20 ml 30 H2O2, mixture produces bubble, and color becomes glassy yellow；
3. standing 12 h, said mixture is filtered, and with the 1 of 1 L:10 watery hydrochloric acid washing, is filtered off except part gold
Belong to ion；Filtering is washed with deionized again, removes unnecessary acid；By obtained solid dissolving in water, then ultrasound makes molten
Liquid is uniformly dispersed, and obtains graphene oxide solution；
4. in addition, at room temperature, by 0.8 g polyvinylpyrrolidones（PVP）It is added to and fills the contracting diethyls two of 50 mL mono-
In the conical flask of alcohol, stir 10 minutes, observation white powder is completely dissolved, and solution is in colourless；Conical flask is placed in oil bath pan,
180 DEG C are increased to temperature, adds 1.2 g SnCl2·2H2O, constant temperature 5-10 minutes；
5. 0.8 g sodium borohydrides are dissolved in 10 mL diglycols, the several seconds is quickly stirred with Dispette
Afterwards, quickly it is added dropwise in above-mentioned conical flask（Diglycol solution rate of addition about 30 drops/minute of sodium borohydride）,
Maintain temperature to stop heating at 180 DEG C, 15 minutes, be cooled to room temperature, with ethanol centrifuge washing 3 times, sample is placed in vacuum and dried
80 DEG C of dryings in case, obtain pure spherical tin simple substance；
6. 0.15 gram of spherical tin simple substance is dispersed in the graphene oxide of 45 milliliter of 2 mg/ml respectively, 1.5 millis are added
36.5wt% hydrochloric acid is risen, is sufficiently stirred, obtains colloidal sol, then by the colloidal sol ultrasonication 3 hours of gained, until forming black
Gel；Transfer the sample into 100 milliliters of ptfe autoclaves, 180 DEG C of constant temperature 8 hours；Question response kettle natural cooling
To room temperature, sample is washed for several times repeatedly with distilled water, that is, obtains tin ash/graphene aerogel；And sample is labeled as
SnO2/GAs-0；
7. by SnO2/ GAs-0 is placed under the titanium window of an electron accelerator of GJ-2- II with 2 MeV accelerating potential and 8
MA electric current, carry out electron beam irradiation with the kGy of dosage 140,280,560,840 respectively（According to irradiation dose, it is respectively designated as：
SnO2/GAs-140, SnO2/GAs-280, SnO2/ GAs-560 and SnO2/GAs-840）.After all samples are freeze-dried 18 h
Lithium ion battery negative material is made.
Method of testing about product electrode material of the present invention
Electrode is according to active material（That is tin ash/graphene aerogel）, conductive agent（Super P）, adhesive is with 8:
1:1 is prepared, and the active material of weighing and conductive agent are placed in mortar and ground 30 minutes, is transferred in 5 mL small beakers,
Adhesive is added, and 1-METHYLPYRROLIDONE 3-5 drops are added dropwise, is sufficiently stirred into slurry.It is 0.3 mm by thickness, a diameter of 14
Mm copper foil is cleaned up with acetone, ethanol reagent, weighs the quality of copper foil, 1-2 drops slurry is added dropwise and in copper foil with liquid-transfering gun
On, it is put into 100-120 DEG C of vacuum drying chamber and dries 12 more than h, take out pole piece, weighs the quality of pole piece.Claimed with every pole piece
Amount quality is multiplied by 0.80 quality as substantial activity material.Using the above-mentioned electrode slice prepared as negative pole, made with lithium metal
For positive pole, electrolyte is LiPF6With the compound of carbonates（Wherein dimethyl carbonate（DMC）：Diethyl carbonate（DEC）：Carbon
Sour ethyl（EC）For 1：1：1）.It is below assembling CR 2032 in the glove box of 1 ppm ar gas environment in moisture and oxygen content
Button cell, circulation and the high rate performance of battery are tested with LAND 2001A battery test systems, and test process keeps constant temperature 25
℃。
Instrument is detected and characterized
Now the instrument detection by the present embodiment products therefrom and characterization result are described below：
SEM detects (FESEM)
With field emission scanning electron microscope (FESEM, model：JSM-6700F, manufacturer：Japan Electronics Corporation)
For observing the surface topography of sample.Fig. 1（a-c）That shown is the SnO prepared by the GO of various concentrations2The airsetting of/graphene
The scanning electron microscope (SEM) photograph in glue section, wherein Fig. 1（a）Middle GO is 5 mg/mL, Fig. 1（b）Middle GO is 3 mg/mL, Fig. 1（c）Middle GO is
2 mg/mL, Fig. 1（d-f）It is in the sample that GO concentration is 2 mg/mL, adds 1.5 mL 36.5wt% hydrochloric acid and prepare
SnO2Basic, normal, high times of scanning electron microscope (SEM) photograph of/graphene aerogel.In Fig. 1（a）In, graphene stacks, and does not form duct
Structure, this is probably to form stronger viscosity because GO concentration is larger.With Fig. 1（a）Compare, Fig. 1（b）Middle duct shape
Into, but be not fully deployed, pore size heterogeneity.Fig. 1（c）As can be seen that now duct is fully deployed, between graphene sheet layer
Intersect stacking, and in loose structure, hole size is about between several microns to more than ten microns.From Fig. 1（c）See graphene film
Layer is not still very thin, and this explanation graphene sheet layer partly overlaps, and is not single-layer graphene film.When in 2 mg/mL graphene oxides
After 1.5 mL 36.5wt% hydrochloric acid of middle addition, such as Fig. 1（d-f）It is shown, it can be found that graphene film is very thin, between lamella mutually
Crosslinking, aperture is more homogeneous, by Fig. 1（f）As can be seen that SnO2Nano particle uniform load is on graphene film, SnO2Particle is big
Small about 3 ~ 5 nm.This unique structure may be caused due to following aspect：When GO concentration is too big, due to viscous
Property enhancing, surface tension is larger, be unfavorable for graphene layering；Simple substance tin generates substantial amounts of hydrogen with hydrochloric acid reaction, gas
Produce the stripping for accelerating graphene sheet layer；The geometry limitation of tin ash particle can improve connecing for interface on graphene film
Touch, so as to suppress the reunion of tin dioxide nano-particle.
Specific surface area and lacunarity analysis (BET)
With specific surface area and lacunarity analysis instrument (BET, model：Full-automatic 4 station, manufacturer：U.S.'s health tower instrument is public
Department) specific surface area and porosity of powder sample obtained by analysis.Fig. 2（a）That shown is SnO2/ GAs-0 nitrogen adsorption desorption
Curve, belong to IV type curves.In 0.43-1.0 P/P0There is an apparent H3 type hysteresis loop in region, and this shows that sample has
Meso-hole structure.Meanwhile H3 type thermoisopleths are considered as related to the hole of platy particle or slit-shaped, for SnO2/ GAs-0 and
Speech, it is likely that the slit between space and stannic oxide particle between graphene sheet layer is relevant.Pore volume is 0.351 cm3·
g−1, it is 364.04 m to be adsorbed by BJH and calculate its specific surface area2·g−1, this uses SnCl than reported in the literature4Or SnCl2
Want high more for tin ash/graphene film prepared by presoma.This further demonstrates that simple substance tin and hydrochloric acid reaction are favourable
In being effectively peeled off for graphene sheet layer, so as to form the less tin ash/graphene aerogel of the number of plies.Larger specific surface area
Be advantageous to improve the chemical property of lithium ion battery, shorter transmission range and more is provided in transmitting procedure for lithium ion
Avtive spot.Fig. 2（b）Shown is graph of pore diameter distribution, and the average pore size of sample is about 3 nanometers, and this is probably derived from graphite
Gap between alkene piece and the nano particle of tin ash.
Thermogravimetric analysis (TG)
With thermogravimetric analysis（Model:STA409PC, TGA, German Netzsch companies）Come research material heat endurance and
Component.Fig. 3 is SnO2/ GAs-0 thermogravimetric weight loss spectrogram, as seen from the figure, 100 DEG C or so of loss is mainly due to sample
The evaporation of moisture and sample Free water in product, is due to the pyrolysis of graphene in 500-600 DEG C of mass loss, by scheming
Spectrum can calculate graphene and account for dry SnO2/ GAs-0 composite samples are always than weighing about 50.7%.
X ray diffraction analysis x (XRD)
With using X-ray diffractometer (INSTRUMENT MODEL：18KW D/MAX2500V+/PC, manufacturer：Rigaku electricity
Machine Co., Ltd.) material phase analysis is carried out to gained powder sample.Non-irradiated and irradiation tin ash/graphene aerogel sample
XRD as shown in figure 4, wherein highest peak is located at (110) crystallographic plane diffraction peak of 2 θ=26.6 °, illustrate that (110) crystal face is dioxy
Change tin preferential growth face, other diffraction maximums respectively 2 θ=33.9,37.9,51.8 and 65.9 °, correspond to Tetragonal dioxy
Change (101), (200), (211) and (301) crystal face of tin（JCPDS41-1445）, the diffraction maximum for not having simple substance tin in figure occurs,
Show that tin has been fully converted to tin ash.According to Scherer equations, calculated from halfwidth, SnO2Particle is averaged
Size about 3.9 nm, SnO2Nanocrystal disperses more uniform, and this is consistent with HRTEM results below.It can be seen that simultaneously
SnO2/ GAs-0 crystallinity is poor, SnO2/ GAs-280 diffraction maximums are stronger, and crystallinity is best, but as irradiation dose is further
Increase, does not occur stronger diffraction maximum.The electron beam irradiation of this explanation doses, be advantageous to improve the crystallization of sample
Property.
Transmission electron microscope detects (TEM)
With Flied emission transmission electron microscope (TEM, model：JEM-2010F, manufacturer：Japan Electronics Corporation) it is right
Gained powder sample carries out microstructure analysis.Fig. 5（a）In be shown SnO2/ GAs-0 low power TEM image, it can send out in figure
Existing tin oxide nano particles are evenly dispersed in the surface of graphene aerosol, large area reunion, SnO do not occur2/GAs-
0th, 140,280,560,840 HRTEM images such as Fig. 5（b）~（f）It is shown.In Fig. 5（b）In, it can indistinctly see some lattice bars
Line picture, illustrate that the crystallinity of sample is weaker, this matches with X-ray diffraction result.From Fig. 5（c）With 5（d）As can be seen that dioxy
Change about 3 ~ 5 nanometers of the particle diameter of tin crystal.Lattice fringe picture is more clear, Fig. 5（d）Crystallinity it is best.Simultaneously as can be seen that stone
Black alkene lamella is very thin, and tin oxide nano particles are evenly distributed on graphenic surface, does not all occur two without the region of graphene
Granules of stannic oxide, further confirm that graphene provides avtive spot for stannic oxide particle growth, while inhibit tin ash
The reunion of particle.When irradiation dose increases to 840 kGy, such as Fig. 5（f）Shown, graphene film fold is remarkably reinforced, SnO2Receive
Rice grain is assembled, while can be seen that multiple-level stack occurs in graphene edge, and this explanation irradiation dose is excessive, destroys graphite
The loose structure of alkene aeroge, makes aeroge cave in, and so as to cause graphene sheet layer to increase, duct is blocked, and this may
It is one of factor for causing its chemical property to reduce.Meanwhile by Fig. 5（d）Illustration can be seen that irradiation dose in 280 kGy
When, there is obvious lattice defect, these defects may be from oxygen vacancy, discomposition and stacking fault, and these defects are
The no chemical property that can influence nano material, it is always that academia has the problem of dispute.As can be seen from the above analysis,
Too high irradiation dose may result in the irradiation damage of sample, and appropriate irradiation will not cause to damage to material, on the contrary can be with
The crystal property of tin ash is improved, while there may be more lattice defects.
Chemical property detects
Electrochemistry is carried out to the button cell after sealing with LAND CT2001A (the blue electric battery test system in Wuhan)
Can test.SnO2/ GAs-140, the electric performance tests of 280,560 and 840 samples as shown in fig. 6, charging/discharging voltage in 0.05-
Between 3.0 V.Fig. 6（a）It is SnO2/ GAs-0 cyclic curve, as can be seen from the figure first discharge capacity up to 2060 mAh
g-1, charging capacity is 1094 mAhg-1, initial coulomb efficiency about 53.11%.Second of discharge capacity is down to 1133 mAhg-1, this is probably due to forming Li2O inorganic solid electrolyte interlayer and the reason of electrochemical dissolution.When circulating for the 10th time,
Discharge capacity is reduced to about 700 mAhg-1, capacity attenuation is obvious.Fig. 6（b）It is putting for irradiation sample and non-irradiated sample
Electric cycle performance, compared with non-irradiated sample, irradiation sample has higher capacity and more preferable cyclical stability, particularly exists
It is obvious after about the 10th circulation.Meanwhile SnO2/ GAs-280 capacity highests, still it can stablize after 50 circulations
In 800 mAhg-1.It is not difficult to find out, irradiation dose is during 0 increases to 280 kGy, the capacity increase of battery, but irradiates agent
For amount during 280 to 840 kGy, capacity does not occur obvious increase.The multiplying power of irradiation sample and non-irradiated sample is followed
Ring such as Fig. 6（c）Shown, current density is from 0.1 to 1 Ag-1.When current density is 0.1A.g-1, non-irradiated sample compares spoke
Product have higher capacity in the same old way, but when current density increases to 0.5 Ag-1With 1 Ag-1When, SnO2/ GAs-280 energy
750 and 450 mAhg are kept respectively-1Specific capacity, this is than the relevant graphene-based tin dioxide composite material reported before
Will height.When current density is reduced to 0.1 Ag-1When, capacity increases to 850 mAhg-1.Meanwhile Fig. 6（d）Show SnO2/
GAs-280 is 0.1 Ag in current density-1When discharge and recharge in show preferable stability.With SnO2/ GAs-0 is compared, to the greatest extent
Manage its first discharge specific capacity and there was only 1680 mAhg-1, compare SnO2/ GAs-0 first discharge specific capacities are low, but its storehouse first
Logical sequence efficiency is higher, reaches 67.2%, while special capacity fade also will more slowly, and second of discharge capacity is 1182 mAhg-1,
Capacity is maintained at 882 mAhg after 10 circulations-1, this will be far above SnO2/GAs-0.So SnO2/ GAs-280 has
Higher reversible capacity.Result above shows, the SnO of irradiation2/ GAs samples have more preferable chemical property, and irradiate agent
When measuring about 280 kGy, chemical property is put up the best performance in irradiation sample.
Infrared spectrometer is analyzed
With Fourier infrared spectrograph（Model：Nicolet 380, FTIR, manufacturer：Sai Mo flies generation, and you are scientific and technological public
Department）Complementary constituent analysis is carried out to the sample of preparation.Fig. 7 is SnO2/GAs-0, SnO2/ GAs-280 and SnO2/GAs-
Fourier's infared spectrum of 840 samples.In 3500 cm-1With 1394 cm-1Position corresponds to the stretching vibration and deformation of hydroxyl respectively
Vibration.For SnO2/ GAs-280 and SnO2For/GAs-840,1394 cm-1Peak is gradually weaker, and this may be with oxygen-containing functional group
Disappearance and graphene oxide are further reduced relevant.1646 cm-1With 1515 cm-1Peak is due to C=O and C=C bending
Caused by vibration.With SnO2/ GAs-0 is compared, SnO2/ GAs-280,840 is in 557 cm-1With 615 cm-1Place occurs substantially
Absworption peak, this forms relevant with Sn-O keys reported in the literature, and this peak is remarkably reinforced explanation by after electron beam irradiation, two
Tin oxide forms stronger interaction with graphene.SnO2/ GAs-280,840 is in 3000-3700 cm-1Peak it is weaker,
Show that hydroxyl is reduced after irradiating, the water content of intramolecular is reduced.The above results show that radiation treatment can remove oxygen-containing official
It can roll into a ball, strengthen the intensity of Sn-O keys, these all may be related to its chemical property.
Raman spectrum analysis
With Raman spectrum（Model:STA409PC, Raman spectrometer Raman, thunder Renishaw companies of Britain）, excite
The nm of wavelength 514.5, power are 3 mW, scanning range：500-1800 cm-1, for the identification of material, the research of molecular structure.
Fig. 8 is SnO2/GAs-0, SnO2/ GAs-280 and SnO2/ GAs-840 Raman collection of illustrative plates.In 1352 cm-1With 1588 cm-1's
Two peaks correspond to carbon material respectivelysp 3 Hydridization andsp 2 Hybrid characteristics are vibrated.1352 cm-1Absworption peak correspond to carbon material
The degree of disorder (is defined as D peaks), and in 1588 cm-1Absworption peak correspond to the degree of graphitization (being defined as G peaks) of carbon material.D peaks
It is due to that G peaks are due to then material planar caused by stretching vibration caused by the space oscillations of unordered induction.Through conventional
ID/IGThe defects of to react carbon material, unordered degree and graphite hydridization degree.In Fig. 8, SnO2The I of/GAs-0 samplesD/IGAbout
1.10 SnO2The I of/GAs-840 samplesD/IGAbout 1.09, SnO2The I of/GAs-280 samplesD/IGAbout 1.06.Wherein SnO2/
GAs-280 changes are obvious, after this change shows appropriate electron beam irradiation,sp 2 The region area of hydridization increases, but hydridization
The quantity in region is reduced.This may be because the hydroxyl of tin ash and graphene, carboxyl, hydrone etc. be in electron beam irradiation condition
Under, the change of stress is generated, causes graphenic surface to generate caused by more atom defect.It is considered that the electricity of appropriateness
Beamlet irradiates, and generates the hydridization of large area, irradiation dose is excessive, and the atom of material may be caused to damage.Therefore, Raman spectrum
Test result and transmission electron microscope, the test result of infrared spectrum it is consistent, material can be produced by indicating appropriate electron beam irradiation
The defects of raw more.
Claims (3)
1. as the irradiated SnO of lithium ion battery2The preparation method of/graphene aerogel nano composite material, it is characterised in that
Have steps of：
A. it is 1 by mass ratio:1 potassium peroxydisulfate and phosphorus pentoxide is dissolved in the appropriate concentrated sulfuric acid, is heated to 80 DEG C, then will
3 grams of native graphites add above-mentioned solution, constant temperature 4 hours；Room temperature is cooled to, after 300~400 milliliters of deionized water dilution,
Stand 12 hours；Washing, filter, dried in 60 DEG C of vacuum drying chambers；
B. obtained precursor is added in 120 milliliters of the ice bath concentrated sulfuric acid, is slowly added into 15 grams of KMnO under agitation4, add
0~5 DEG C is maintained the temperature at during entering；Then by temperature control in 35 DEG C of stirrings to abundant reaction；Add 250~300 millis
Deionized water dilution is risen, temperature is less than 5 DEG C in ice bath in dilution；700 ml deionized waters are added after stirring,
And it is added immediately 20 milliliter 30% of H2O2, mixture produces bubble, and color becomes glassy yellow；
C. 12 hours are stood, said mixture is filtered, and with the 1 of 1 liter:10 watery hydrochloric acid washing, is filtered off except part metals
Ion；Filtering is washed with deionized again, removes unnecessary acid；By obtained solid dissolving in water, then ultrasound makes solution
It is uniformly dispersed, obtains graphene oxide solution；
D. in addition, at room temperature, 0.8 gram of polyvinylpyrrolidone (PVP) is added to and fills 50 milliliters of diglycols
In conical flask, stir 10 minutes, observation white powder is completely dissolved, and solution is in colourless；Conical flask is placed in oil bath pan, to temperature
Degree is increased to 180 DEG C, adds 1.2 grams of SnCl2·2H2O, constant temperature 5-10 minutes；
E. 0.8 gram of sodium borohydride is dissolved in 10 milliliters of diglycols, after quickly stirring the several seconds with Dispette, soon
Speed is added dropwise in above-mentioned conical flask, and the diglycol solution rate of addition of sodium borohydride is 30 drops/minute；Maintain temperature
Degree is at 160-180 DEG C, 10-25 minutes, stops heating, is cooled to room temperature, and with ethanol centrifuge washing 3 times, sample is placed in into vacuum
80 DEG C of dryings in baking oven, obtain pure spherical tin simple substance；
F.0.15 gram spherical tin simple substance is dispersed in the graphene oxide of 45 milliliter of 2 mg/ml respectively, adds 1.5 milliliters
36.5wt% hydrochloric acid, is sufficiently stirred, and obtains colloidal sol, then by the colloidal sol ultrasonication 3 hours of gained, until forming black
Gel；Transfer the sample into 100 milliliters of ptfe autoclaves, 180 DEG C of constant temperature 8 hours；Question response kettle naturally cools to
Room temperature, sample is washed for several times repeatedly with distilled water, that is, obtains tin ash/graphene aerogel；And sample is labeled as
SnO2/GAs-0；
G. by SnO2/ GAs-0 is placed under the titanium window of an electron accelerator of GJ-2- II with 2MeV accelerating potential and 8mA electricity
Stream, electron beam irradiation is carried out with dosage 140,280,560,840kGy respectively, according to irradiation dose, is respectively designated as：SnO2/
GAs-140,SnO2/GAs-280,SnO2/ GAs-560, and SnO2/ GAs-840, all samples are made after being freeze-dried 18 hours
Lithium ion battery negative material.
2. the irradiated SnO of lithium ion battery according to claim 12The preparation of/graphene aerogel nano composite material
Method, it is characterised in that：In step f, it can equally be prepared using the graphene oxide of 45 milliliters of 3 or 5 mg/mls
SnO2/GAs-0。
3. the irradiated SnO of lithium ion battery according to claim 12The preparation of/graphene aerogel nano composite material
Method, it is characterised in that：In step a, the addition of potassium peroxydisulfate and phosphorus pentoxide is 2.5 grams.
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| 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 |
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