CN108630911A - A kind of SnO of oxygen-containing vacancy defect2Graphene nanocomposite material and application in room temperature sodium-ion battery cathode - Google Patents
A kind of SnO of oxygen-containing vacancy defect2Graphene nanocomposite material and application in room temperature sodium-ion battery cathode Download PDFInfo
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- CN108630911A CN108630911A CN201810175614.1A CN201810175614A CN108630911A CN 108630911 A CN108630911 A CN 108630911A CN 201810175614 A CN201810175614 A CN 201810175614A CN 108630911 A CN108630911 A CN 108630911A
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- oxygen
- nanocomposite material
- sodium
- containing vacancy
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- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 58
- 239000001301 oxygen Substances 0.000 title claims abstract description 58
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000000463 material Substances 0.000 title claims abstract description 53
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 47
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 29
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 56
- 230000007547 defect Effects 0.000 claims abstract description 53
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 16
- 229910052708 sodium Inorganic materials 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011889 copper foil Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 235000019241 carbon black Nutrition 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 230000009514 concussion Effects 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 claims 1
- -1 oxygen Graphite alkene Chemical class 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 238000003860 storage Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000005496 tempering Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000008278 dynamic mechanism Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
-
- 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 present invention discloses a kind of SnO of oxygen-containing vacancy defect2Graphene nanocomposite material and application in room temperature sodium-ion battery cathode.The present invention prepares SnO first using hydro-thermal method2Graphene nanocomposite material, then again by way of being tempered in weakly reducing atmosphere, to SnO2Nanocrystalline middle introducing Lacking oxygen defect.Using oxygen-containing vacancy defect SnO made from this method2Graphene nanocomposite material shows extremely outstanding high rate performance and cyclical stability when for sodium-ion battery cathode.
Description
Technical field
The invention belongs to technical field of nano material, and in particular to a kind of SnO of oxygen-containing vacancy defect2Graphene nano
The preparation method of composite material and application in room temperature sodium-ion battery cathode.
Background technology
Battery technology has obtained significant progress in the past 20 years, and lithium ion battery is with higher energy density, outstanding
Charge-discharge performance and good service life, have captured the markets such as mobile terminal device, computer, mobile phone, electric vehicle.With
The continuous expansion of the lithium ion battery market demand, the whole world constantly increase the dependence of clean energy resource, and the exploitation of lithium resource is not for
Should ask, when the river rises the boat goes up for the prices of raw materials, industry gradually begins look for the substitute of lithium ion battery.In order to solve this problem,
Industry proposes to substitute elemental lithium, the cheap sodium-ion battery of development cost using the close sodium element of chemical property.Compared to lithium from
The raw material sources of sub- battery, sodium-ion battery are extremely abundant and cheap, more sensitive for prices such as extensive energy storage
Field when, can significantly reduce the energy storage cost of unit watt-hour (Wh).Sodium-ion battery application prospect is vast, but does not have always
Have and obtain conclusive breakthrough, reason, which is existing negative material still, cannot meet sodium-ion battery for charge-discharge velocity
With the demand of cycle life.With SnO2Novel anode material for representative is the ion battery electrode material of very promising a new generation
Material, it has the advantages that, and specific capacity height, charge and discharge platform is stable, safety is good, long lifespan, resourceful etc. a series of.But
SnO2There is a problem of that cyclical stability is poor, the internal stress caused by volume expansion be easy to cause electrode in charge and discharge
" reunion " and " broken " causes the poor contact of the part of electrode active material, leads to the rapid decrease of material electrochemical performance.
Simultaneously as the ionic radius of sodium is larger, it is difficult to embedded SnO2Lattice voids in, therefore its reaction dynamic mechanism is mainly
The slow linear flooding mechanism of semo-infinite, causes the rate charge-discharge performance of this kind of material poor.
To improve SnO2The storage sodium cyclical stability and high rate performance of electrode material, researcher both domestic and external have done largely
Trial, it is considered as more effective means to build composite material and nanosizing.Structure composite material can buffer in charge and discharge
SnO2The stress that the volume change of particle is brought inhibits reunion pulverizing problem, achievees the purpose that improve storage sodium cyclical stability；And
Nanosizing can promote the diffusion rate of sodium ion, improve reaction rate.Make SnO by building nanocomposite2Electrode material
Storage sodium cycle life be significantly enhanced, but even by SnO2Particle has been reduced to Nano grade, charge-discharge velocity is slow,
The problem of high rate performance difference still cannot efficiently solve, and hinder the commercialization process of such material.
Invention content
It is an object of the invention in view of the deficiencies of the prior art, provide a kind of oxygen-containing vacancy defect SnO2Graphene
Nanocomposite.Utilize the easily embedded SnO of sodium ion2The kinetics machine during sodium is stored up in the property of lattice defect, transformation
System, to improve the rate charge-discharge performance of material.The present invention prepares SnO first using hydro-thermal method2Graphene nano composite wood
Material, then again by way of being tempered in weakly reducing atmosphere, to SnO2Nanocrystalline middle introducing Lacking oxygen defect.Using this method
Oxygen-containing vacancy defect SnO obtained2When graphene nanocomposite material is used for sodium-ion battery cathode, it is excellent to show extremely position
Elegant high rate performance and cyclical stability, further demonstrates the feasibility of the invention.
In order to solve the above-mentioned technical problem, the present invention is addressed by following technical proposals：
A kind of oxygen-containing vacancy defect SnO2Graphene composite material, by the following method step be prepared：
Step (1), by 100~300mg SnCl4·5H2O is dissolved into 15ml pure water, is stirred evenly；Take 5~10ml dense
Degree is the graphene oxide water solution of 2mg/ml, is slowly dropped to SnCl4In solution, it is placed in ultrasonic bath at room temperature at 25 DEG C
15~30min of middle concussion obtains filemot transparent clear solution.
Graphene oxide and SnCl4Mass ratio be (10-20):(74.3-222.9).
The solution that step (1) obtains is packaged in 50ml hydrothermal reaction kettles by step (2), is heated to 140-160 DEG C, is protected
Temperature 16~for 24 hours.
Step (3), by step (2), treated that (5000~7000rpm, 5~10min) is centrifuged in solution, inclines
Gained sediment is placed in baking oven after removing supernatant liquor body, 50~80 DEG C of vacuum drying 12-16h.
Step (4), by step (3) obtain dried powder be placed in atmosphere protection tube furnace, at 400-600 DEG C into
Row temper, while it being passed through reducibility gas, in 50-800 ml/min, processing time is 3~5 hours for gas flow rate control,
Obtain required oxygen-containing vacancy defect SnO2Graphene nanocomposite material
Preferably, the reducibility gas that step (4) is passed through is to contain 3-8vol.%H2H2/ Ar gaseous mixtures.
It is a further object to provide above-mentioned oxygen-containing vacancy defect SnO2Graphene nanocomposite material is in room temperature
Application on sodium-ion battery cathode.
By present invention oxygen-containing vacancy defect SnO obtained above2Graphene nanocomposite material is made electrode and is assembled into
Sodium ion tests battery, to evaluate the high rate performance, capacity and stable charge/discharge of electrode.
Preferably, electrode uses oxygen-containing vacancy defect SnO obtained2Graphene nanocomposite material sample, Super
P carbon blacks and PVDF are with 75:15:The ratio of 10wt.% mixes, and paste is tuned into nmp solvent, is coated in copper foil surface, waits for vacuum
After drying, coating copper foil is cut into the disk of a diameter of 15mm as sodium-ion battery electrode.Select sodium-ion battery electricity consumption
Solve liquid (EC:PC=1:1, NaClO4A concentration of 1mol/L) and metallic sodium paillon be used as to electrode.
Preferably, the capacity of sodium-ion battery is tested using constant current charge-discharge method, electric current that when test selects
Density is 40mA/g, and charge and discharge potential executes cycle 50 times from 0.05-3V.
Preferably, the current density that the high rate performance test of sodium-ion battery is selected is respectively 40,100,240,600,
1200mA/g, charge and discharge potential execute cycle 10 times from 0.05-3V, every group of current density.
Preferably, the burn-in test of sodium-ion battery is tested using constant current charge-discharge method, what when test selected
Current density is 40mA/g, and charge and discharge potential executes cycle 300 times from 0.05-3V.
The present invention has the characteristics that following：
The present invention provides a kind of oxygen-containing vacancy defect SnO2The preparation method of graphene nanocomposite material, it is sharp first
SnO is obtained with hydrothermal method2Graphene nanocomposite material, then by being tempered in weak reducing atmosphere, to SnO2
Lacking oxygen defect is introduced in nanocrystal.
The oxygen-containing vacancy defect SnO that the present invention obtains2Graphene nanocomposite material has as sub- cell negative electrode material
The features such as capacity is big, good rate capability, good cycle, long service life.SnO first2Graphene nanocomposite material carries
Good microstructural stability has been supplied, has been conducive to obtain longer cycle life.Secondly, the Lacking oxygen defect of introducing will originally
Reaction dynamic mechanism based on linearly being spread with semo-infinite changes into the embedded and linear diffusion blender system of semo-infinite, thus aobvious
The rate for improving reaction write, improves the high rate performance of charge and discharge process.
Description of the drawings
Fig. 1 is scanning electron microscope (SEM) figure of sample：(a) 1 oxygen-containing vacancy defect SnO of embodiment2Graphene nano is compound
Material, (b) comparative example.
Fig. 2 is transmission electron microscope (TEM) figure of sample：(a) 1 oxygen-containing vacancy defect SnO of embodiment2Graphene nano is compound
Material, (b) comparative example；
Fig. 3 is oxygen-containing vacancy defect SnO prepared by the present invention2The X-ray of graphene nanocomposite material and comparative example is spread out
Penetrate (XRD) collection of illustrative plates；
Fig. 4 is oxygen-containing vacancy defect SnO prepared by the present invention2The Raman of graphene nanocomposite material and comparative example
(Raman) spectrum, (a) spectral region 500-2000cm-1, (b) spectral region 300-800 cm-1；
Fig. 5 is oxygen-containing vacancy defect SnO prepared by the present invention2The X-ray light of graphene nanocomposite material and comparative example
Electron spectrum (XPS) collection of illustrative plates；
Fig. 6 is oxygen-containing vacancy defect SnO prepared by the present invention2Graphene nanocomposite material and comparative example make sodium ion
Specific energy density-cycle-index collection of illustrative plates when battery cathode；
Fig. 7 is oxygen-containing vacancy defect SnO prepared by the present invention2Graphene nanocomposite material and comparative example make sodium ion
High rate performance collection of illustrative plates when battery cathode；
Fig. 8 is oxygen-containing vacancy defect SnO prepared by the present invention2Graphene nanocomposite material makees sodium-ion battery cathode
When ageing of performance test map.
Specific implementation mode
The present invention is further analyzed With reference to embodiment.
Embodiment 1, oxygen-containing vacancy defect SnO2The preparation of graphene nanocomposite material.
A.SnO2The synthesis of graphene nanocomposite material：By 200mg SnCl4·5H2O is dissolved into 15ml pure water,
It stirs evenly；The graphene oxide water solution for taking a concentration of 2mg/ml of 10ml, is slowly dropped to SnCl4In solution, 25 DEG C of rooms
It is placed in ultrasonic bath under temperature and shakes 30min, obtain filemot transparent clear solution.The solution of acquisition is packaged in 50ml water
In thermal response kettle, 160 DEG C are heated to, keeps the temperature 20h.Solution after hydro-thermal process is centrifuged (7000rpm,
10min), incline and gained sediment is placed in baking oven after supernatant liquor body, 60 DEG C of vacuum drying 16h.
B. temper：The dried powder of acquisition is placed in atmosphere protection tube furnace, is carried out at tempering at 600 DEG C
Reason, while being passed through containing 3vol.%H2H2/ Ar mixed gas, in 100ml/min, processing time is 3 small for gas flow rate control
When, to introduce Lacking oxygen defect.
Comparative example, not oxygen-containing vacancy defect SnO2The preparation of graphene nanocomposite material.
A.SnO2The synthesis of graphene nanocomposite material：By 200mg SnCl4·5H2O is dissolved into 15ml pure water,
It stirs evenly；The graphene oxide water solution for taking a concentration of 2mg/ml of 10ml, is slowly dropped to SnCl4In solution, 25 DEG C of rooms
It is placed in ultrasonic bath under temperature and shakes 30min, obtain filemot transparent clear solution.The solution of acquisition is packaged in 50ml water
In thermal response kettle, 160 DEG C are heated to, keeps the temperature 20h.(7000rpm, 10min) is centrifuged in solution after hydro-thermal process,
Incline and gained sediment is placed in baking oven after supernatant liquor body, 60 DEG C of vacuum drying 16h.
B. temper：The dried powder of acquisition is placed in atmosphere protection tube furnace, is carried out at tempering at 600 DEG C
Reason, while it being passed through high-purity Ar gas, in 100ml/min, processing time is 3 hours for gas flow rate control.
It is observed that the oxygen-containing vacancy defect SnO prepared2Graphene nanocomposite material has typical graphene
The microscopic appearance structure (Fig. 1 (a)) of class nanocomposite, lamellar structure is graphite olefinic constituent, and nanoparticles are
SnO2Particle.Compared with comparative example (Fig. 1 (b)), oxygen-containing vacancy defect SnO made from embodiment 12Graphene nano is compound
Material shows more folds and hole on microscopic appearance, and reason may be the graphene oxide under weak reducing atmosphere
It is more fully restored, more oxygen-containing class group valence links is caused to be broken.It can be seen by the TEM pictures (Fig. 2) of sample
It arrives, oxygen-containing vacancy defect SnO2The SnO of graphene nanocomposite material2Crystal grain shows more fuzzy boundary, passes through high score
Resolution transmission electron microscope (HRTEM's) further looks at, in SnO2(110) crystal face on there is many cavities, it was demonstrated that oxygen is empty
Position defect is introduced into；And the SnO of comparative example2Crystal grain then shows more apparent boundary, and the Atomic Arrangement on crystal face is more whole
Together, defect is less.X-ray diffraction (XRD) collection of illustrative plates (Fig. 3) after sample temper proves to introduce the SnO of Lacking oxygen defect2Still
So show typical metasimpsonite structure SnO2.Raman spectrum analysis (Fig. 4) shows to carry out temper in reducing atmosphere
Influence for graphite olefinic constituent is smaller, only the slight variations peak intensity ratio (Fig. 4 (a)) of graphite features peak D and G；For
SnO2Nanocrystalline component introduces after defect in 473cm-1There is a wave crest in position, is SnO2EgRaman-active vibrational mode,
Demonstrate the presence of Lacking oxygen defect.Sample analyzes the bonding state of its contained compound by x-ray photoelectron spectroscopy (XPS)
(Fig. 5), experimental result further prove the Sn in sample there are the valence state (Fig. 5 (b)) other than 4 valences, and graphene oxide is in H2/
The presence (Fig. 5 (d)) of more thorough (Fig. 5 (c)) and Lacking oxygen defect for being reduced in Ar mixed atmospheres.Above experiment
Conclusion is mutually consistent, fully proves oxygen-containing vacancy defect SnO2Graphene nanocomposite material is successfully prepared.
Application Example 2, oxygen-containing vacancy defect SnO2The storage sodium performance test of graphene nanocomposite material
By oxygen-containing vacancy defect SnO made from embodiment 12Graphene nanocomposite material and reference examples respectively with Super
P carbon blacks and PVDF are with 75:15:The ratio of 10wt.% mixes, and paste is tuned into nmp solvent, is coated in copper foil surface, waits for vacuum
After drying, coating copper foil is cut into the disk of a diameter of 15mm as sodium-ion battery electrode.Select sodium-ion battery electricity consumption
Solve liquid (EC:PC=1:1, NaClO4A concentration of 1mol/L) and metallic sodium paillon be used as to electrode, be assembled into glove box
RC2030 type button cells carry out constant current charge-discharge test in Neware BTS battery test systems.The appearance of sodium-ion battery
Pilot production is measured to be tested with constant current charge-discharge method, the current density that when test selects is 40mA/g, charge and discharge potential from
0.05-3V, executes cycle 50 times.High rate performance test executes after being recycled at 50 times, and the current density of selection is respectively 40,100,
240,600,1200mA/g, charge and discharge potential executes cycle 10 times from 0.05-3V, every group of current density.Sodium-ion battery it is old
Change test to be tested using constant current charge-discharge method, the current density that when test selects is 40mA/g, charge and discharge potential from
0.05-3V, executes cycle 300 times.In conjunction with Fig. 6, Fig. 7 and Fig. 8 it can be seen that, when which is used as sodium-ion battery cathode, and not
The comparative example of oxygen-containing vacancy defect, which compares, shows good storage sodium capacity (530mAh/g, current density 40mA/g), times
Rate performance (391mAh/g, current density 1200mA/g) and cycle life (>=500mAh/g, 300 cycles).
Embodiment 2, oxygen-containing vacancy defect SnO2The preparation of graphene nanocomposite material.
A.SnO2The synthesis of graphene nanocomposite material：By 100mg SnCl4·5H2O is dissolved into 15ml pure water,
It stirs evenly；The graphene oxide water solution for taking a concentration of 2mg/ml of 5ml, is slowly dropped to SnCl4In solution, in 25 DEG C of room temperatures
Under be placed in ultrasonic bath and shake 15min, obtain filemot transparent clear solution.The solution of acquisition is packaged in 50ml hydro-thermals
In reaction kettle, 140 DEG C are heated to, heat preservation is for 24 hours.(5000rpm, 10min) is centrifuged in solution after hydro-thermal process, is inclined
Gained sediment is placed in baking oven after removing supernatant liquor body, 80 DEG C of vacuum drying 12h.
B. temper：The dried powder of acquisition is placed in atmosphere protection tube furnace, is carried out at tempering at 400 DEG C
Reason, while being passed through containing 8vol.%H2H2/ Ar mixed gas, in 800ml/min, processing time is 3 small for gas flow rate control
When, to introduce Lacking oxygen defect.
The oxygen-containing vacancy defect SnO of preparation2Graphene nanocomposite material is similar to Example 1, has typical graphite
The microscopic appearance structure of alkenes nanocomposite, lamellar structure is graphite olefinic constituent, and nanoparticles are SnO2Particle.
More fold and hole are showed on microscopic appearance, in SnO2Crystal face on there is many cavities, it was demonstrated that Lacking oxygen
Defect is introduced into.
When the material is used as sodium-ion battery cathode, shown compared with the not comparative example of oxygen-containing vacancy defect good
Storage sodium capacity (480mAh/g, current density 40mA/g), high rate performance (324mAh/g, current density 1200mA/g) and cycle
Service life (>=430mAh/g, 300 cycles).
Embodiment 3, oxygen-containing vacancy defect SnO2The preparation of graphene nanocomposite material.
A.SnO2The synthesis of graphene nanocomposite material：By 300mg SnCl4·5H2O is dissolved into 15ml pure water,
It stirs evenly；The graphene oxide water solution for taking a concentration of 2mg/ml of 8ml, is slowly dropped to SnCl4In solution, in 25 DEG C of room temperatures
Under be placed in ultrasonic bath and shake 25min, obtain filemot transparent clear solution.The solution of acquisition is packaged in 50ml hydro-thermals
In reaction kettle, 150 DEG C are heated to, keeps the temperature 16h.(6000rpm, 6min) is centrifuged in solution after hydro-thermal process, is inclined
Gained sediment is placed in baking oven after removing supernatant liquor body, 50 DEG C of vacuum drying 16h.
B. temper：The dried powder of acquisition is placed in atmosphere protection tube furnace, is carried out at tempering at 500 DEG C
Reason, while being passed through containing 5vol.%H2H2/ Ar mixed gas, in 50ml/min, processing time is 5 small for gas flow rate control
When, to introduce Lacking oxygen defect.
The oxygen-containing vacancy defect SnO of preparation2Graphene nanocomposite material is similar to Example 1, has typical graphite
The microscopic appearance structure of alkenes nanocomposite, lamellar structure is graphite olefinic constituent, and nanoparticles are SnO2Particle.
More fold and hole are showed on microscopic appearance, in SnO2Crystal face on there is many cavities, it was demonstrated that Lacking oxygen
Defect is introduced into.
When the material is used as sodium-ion battery cathode, shown compared with the not comparative example of oxygen-containing vacancy defect good
Storage sodium capacity (473mAh/g, current density 40mA/g), high rate performance (311mAh/g, current density 1200mA/g) and cycle
Service life (>=427mAh/g, 300 cycles).
In short, sode cell application described above is only presently preferred embodiments of the present invention, it is all according to scope of the present invention patent
Made by equivalent changes and modifications, should all belong to the covering scope of patent of the present invention.
Claims (5)
1. a kind of SnO of oxygen-containing vacancy defect2Graphene nanocomposite material, by the following method step be prepared, it is special
Sign is：
Graphene oxide water solution is slowly dropped to SnCl by step (1)4In solution, it is placed in ultrasonic bath at room temperature at 25 DEG C
15~30min of middle concussion obtains filemot transparent clear solution；
The solution that step (1) obtains is packaged in 50ml hydrothermal reaction kettles by step (2), is heated to 140-160 DEG C, heat preservation 16
~for 24 hours；
Step (3), by step (2), treated, and solution is centrifuged, and sets gained sediment after the supernatant liquor body that inclines
In baking oven, 50~80 DEG C of vacuum drying 12-16h；
The dried powder that step (3) obtains is placed in atmosphere protection tube furnace by step (4), is tempered at 400-600 DEG C
Processing, while it being passed through reducibility gas, gas flow rate control is 3~5 hours in 50-800ml/min, processing time, obtains institute
The oxygen-containing vacancy defect SnO needed2Graphene nanocomposite material；The reducibility gas being wherein passed through is to contain 3-8vol.%H2
H2/ Ar gaseous mixtures.
2. a kind of SnO of oxygen-containing vacancy defect as described in claim 12Graphene nanocomposite material, it is characterised in that oxygen
Graphite alkene and SnCl4Mass ratio be (10-20):(74.3-222.9).
3. a kind of SnO of oxygen-containing vacancy defect as described in claim 12Graphene nanocomposite material, it is characterised in that step
Suddenly (3) centrifugal condition is 5000~7000rpm of rotating speed, 5~10min of centrifugation time.
4. a kind of SnO of oxygen-containing vacancy defect as described in claim 12Graphene nanocomposite material is in room temperature sodium ion electricity
Application on the cathode of pond.
5. application as claimed in claim 4, it is characterised in that specifically use oxygen-containing vacancy defect as described in claim 1
SnO2Graphene nanocomposite material and Super P carbon blacks, PVDF are with 75:15:The ratio of 10wt% mixes；Use nmp solvent
Be tuned into paste, be coated in copper foil surface, after being dried in vacuo, using coating copper foil cut into the disk of a diameter of 15mm as sodium from
Sub- battery electrode；Wherein select sodium-ion battery electrolyte (EC:PC=1:1, NaClO4A concentration of 1mol/L) and metallic sodium
Paillon is used as to electrode.
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| CN110085821A (en) * | 2019-04-17 | 2019-08-02 | 杭州电子科技大学 | A kind of novel SnO2The preparation method of graphene room temperature anode material of lithium-ion battery |
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| CN113851638B (en) * | 2021-08-27 | 2023-02-10 | 华东理工大学 | SnO (stannic oxide) 2-x Preparation method and application thereof, and composite electrode |
| CN114455630A (en) * | 2022-02-28 | 2022-05-10 | 哈尔滨工业大学（威海） | Multi-band composite electromagnetic wave absorption material and preparation method and application thereof |
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