CN108630911B - SnO containing oxygen vacancy defects2-graphene nanocomposites and uses thereof - Google Patents
SnO containing oxygen vacancy defects2-graphene nanocomposites and uses thereof Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 69
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 56
- 239000001301 oxygen Substances 0.000 title claims abstract description 56
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 53
- 230000007547 defect Effects 0.000 claims abstract description 44
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 26
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 18
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 13
- 238000005496 tempering Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 2
- 239000002159 nanocrystal Substances 0.000 abstract description 3
- 238000000137 annealing Methods 0.000 abstract 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 20
- 229910052708 sodium Inorganic materials 0.000 description 14
- 239000011734 sodium Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 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 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 238000007599 discharging Methods 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000007600 charging Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 238000010335 hydrothermal treatment Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000007709 nanocrystallization Methods 0.000 description 2
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- 238000011056 performance test Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
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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
- H01M10/054—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
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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
- H01M4/58—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 invention discloses a SnO 2-graphene nano composite material containing oxygen vacancy defects and application thereof. The invention adopts a hydrothermal method to prepare SnO firstly2-graphene nanocomposites and then annealing to SnO in a weakly reducing atmosphere2Oxygen vacancy defects are introduced into the nanocrystals. Oxygen vacancy defect-containing SnO prepared by adopting method2The graphene nanocomposite shows extremely excellent rate performance and cycle stability when used for a sodium ion battery negative electrode.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to SnO with oxygen vacancy defects2A preparation method of the graphene nanocomposite and application of the graphene nanocomposite to a cathode of a sodium ion battery at normal temperature.
Background
In recent 20 years, battery technology has been developed, and lithium ion batteries occupy markets such as mobile terminal devices, computers, mobile phones, electric vehicles and the like due to high energy density, excellent charge and discharge performance and good service life. With the continuous expansion of the market demand of lithium ion batteries and the continuous increase of global dependence on clean energy, the shortage of exploitation and supply of lithium resources and the rise of raw material price and water, the industry gradually begins to find a substitute of the lithium ion batteries. In order to solve the problem, the industry proposes to use sodium element with close chemical properties to replace lithium element and develop a sodium ion battery with low cost. Compared with a lithium ion battery, the sodium ion battery has the advantages of abundant raw material sources and low price, and can greatly reduce the energy storage cost per watt hour (Wh) when being used in the fields with sensitive prices such as large-scale energy storage and the like. The sodium ion battery has wide application prospectHowever, the current negative electrode materials still cannot meet the requirements of the sodium ion battery on the charge and discharge rate and the cycle life. In SnO2The novel cathode material is a potential new-generation ion battery electrode material and has a series of advantages of high specific capacity, stable charge and discharge platform, good safety, long service life, abundant resources and the like. However, SnO2The problem of poor cycling stability exists, the internal stress caused by volume expansion during charging and discharging is easy to cause the agglomeration and the breakage of the electrode, the partial poor contact of the electrode active material is caused, and the electrochemical performance of the material is rapidly reduced. Meanwhile, sodium has a large ionic radius and is difficult to be embedded into SnO2The reaction kinetic mechanism of the material is mainly a slow semi-infinite linear diffusion mechanism, so that the rate charge and discharge performance of the material is poor.
For improving SnO2The sodium storage cycle stability and rate capability of the electrode material are greatly tried by researchers at home and abroad, and the construction of the composite material and the nanocrystallization are considered to be effective means. SnO capable of buffering in charging and discharging process for constructing composite material2Stress caused by volume change of the particles inhibits the problem of agglomeration and pulverization, and the aim of improving the sodium storage cycle stability is fulfilled; and the nanocrystallization can promote the diffusion rate of sodium ions and improve the reaction rate. SnO by construction of nanocomposites2The sodium storage cycle life of the electrode material is greatly prolonged, but even SnO is reduced2The particles are reduced to a nanometer level, the problems of slow charge and discharge rate and poor rate performance can not be effectively solved, and the commercialization process of the materials is hindered.
Disclosure of Invention
It is an object of the present invention to overcome the disadvantages of the prior art by providing a SnO having oxygen vacancy defects2-graphene nanocomposites. SnO easy to embed by sodium ions2The property of lattice defect changes the reaction kinetic mechanism in the process of storing sodium, so as to improve the multiplying power charge-discharge performance of the material. The invention adopts a hydrothermal method to prepare SnO firstly2-graphene nanocompositesCharging, and tempering in weak reducing atmosphere to SnO2Oxygen vacancy defects are introduced into the nanocrystals. Oxygen vacancy defect-containing SnO prepared by adopting method2When the graphene nanocomposite is used for a sodium ion battery cathode, excellent rate performance and cycle stability are shown, and the feasibility of the invention is further proved.
In order to solve the technical problem, the invention is solved by the following technical scheme:
oxygen vacancy defect SnO2-a graphene composite material, prepared by the following method steps:
step (1), adding 100-300 mg SnCl4·5H2Dissolving O in 15ml of pure water, and uniformly stirring; taking 5-10 ml of graphene oxide aqueous solution with the concentration of 2mg/ml, and slowly dropwise adding the graphene oxide aqueous solution to SnCl4And placing the solution in an ultrasonic washing tank at the room temperature of 25 ℃ and oscillating for 15-30 min to obtain a yellow brown transparent clear solution.
Graphene oxide and SnCl4The mass ratio of (10-20) to (74.3-222.9).
And (2) packaging the solution obtained in the step (1) in a 50ml hydrothermal reaction kettle, heating to 140 ℃ and 160 ℃, and preserving heat for 16-24 hours.
And (3) carrying out centrifugal separation (5000-7000 rpm for 5-10 min) on the solution treated in the step (2), pouring out supernatant liquid, placing the obtained precipitate in an oven, and carrying out vacuum drying at 50-80 ℃ for 12-16 h.
Step (4) placing the dry powder obtained in the step (3) in an atmosphere protection tube furnace, tempering at the temperature of 400-600 ℃, introducing reducing gas, controlling the gas flow rate at 50-800 ml/min, and treating for 3-5 hours to obtain the required SnO with oxygen vacancy defects2-graphene nanocomposites
Preferably, the reducing gas introduced in step (4) contains 3-8 vol.% H2H of (A) to (B)2and/Ar mixed gas.
It is another object of the present invention to provide the above-mentioned SnO having oxygen vacancy defects2Application of the graphene nanocomposite to a cathode of a normal-temperature sodium-ion battery.
The oxygen-containing vacancy defect SnO prepared by the invention2And preparing the graphene nano composite material into an electrode and assembling the electrode into a sodium ion test battery so as to evaluate the rate capability, capacity and charge-discharge stability of the electrode.
Preferably, the electrode is made of oxygen vacancy defect-containing SnO2Mixing a graphene nanocomposite sample, SuperP carbon black and PVDF in a ratio of 75:15:10 wt.%, blending into paste with an NMP solvent, coating on the surface of a copper foil, and cutting the coated copper foil into a wafer with the diameter of 15mm after vacuum drying to serve as a sodium-ion battery electrode. Electrolyte for sodium ion battery (EC: PC ═ 1:1, NaClO) is selected4Concentration of 1mol/L) and a metallic sodium foil as a counter electrode.
Preferably, the capacity of the sodium ion battery is tested by adopting a constant current charging and discharging method, the current density selected during the test is 40mA/g, the charging and discharging potential is from 0.05V to 3V, and the cycle is executed for 50 times.
Preferably, the current densities selected for the rate performance test of the sodium ion battery are respectively 40,100,240,600 and 1200mA/g, the charge-discharge potential is from 0.05 to 3V, and each group of current densities performs 10 times of circulation.
Preferably, the aging test of the sodium ion battery is carried out by adopting a constant current charging and discharging method, the current density selected during the test is 40mA/g, the charging and discharging potential is 0.05-3V, and the cycle is executed for 300 times.
The invention has the following characteristics:
the invention provides oxygen vacancy defect-containing SnO2The preparation method of the-graphene nano composite material comprises the steps of firstly obtaining SnO by using a hydrothermal method2Graphene nanocomposites and subsequent tempering in a weakly reducing atmosphere to SnO2Oxygen vacancy defects are introduced into the nanocrystals.
The oxygen-containing vacancy defect SnO obtained by the invention2The graphene nanocomposite as a cathode material of a sub-battery has the characteristics of large capacity, good rate capability, good cycle performance, long service life and the like. First SnO2The graphene nanocomposite provides good microstructural stability, which is beneficial for obtainingLonger cycle life. And secondly, the introduced oxygen vacancy defect changes the reaction kinetic mechanism which mainly takes semi-infinite linear diffusion originally into an embedding and semi-infinite linear diffusion mixed mechanism, so that the reaction rate is obviously improved, and the rate capability in the charging and discharging process is improved.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a sample: (a) EXAMPLE 1 oxygen vacancy defect-containing SnO2Graphene nanocomposite material, (b) comparative example.
FIG. 2 is a Transmission Electron Microscope (TEM) image of a sample: (a) EXAMPLE 1 oxygen vacancy defect-containing SnO2-graphene nanocomposite, (b) comparative example;
FIG. 3 shows oxygen vacancy defect-containing SnO prepared by the present invention2-X-ray diffraction (XRD) patterns of graphene nanocomposites and comparative examples;
FIG. 4 shows oxygen vacancy defect-containing SnO prepared by the present invention2Raman (Raman) spectra of graphene nanocomposites and comparative examples, (a) spectral range 500--1(b) a spectral range of 300-800 cm-1；
FIG. 5 shows oxygen vacancy defect-containing SnO prepared by the present invention2-X-ray photoelectron spectroscopy (XPS) spectra of graphene nanocomposites and comparative examples;
FIG. 6 shows oxygen vacancy defect-containing SnO prepared by the present invention2-specific energy density-cycle number map of the graphene nanocomposite and the comparative example when they are used as the negative electrode of a sodium ion battery;
FIG. 7 shows oxygen vacancy defect-containing SnO prepared by the present invention2-a rate performance map of the graphene nanocomposite and the comparative example when they are used as a sodium ion battery negative electrode;
FIG. 8 shows oxygen vacancy defect-containing SnO prepared by the present invention2-performance aging test pattern of graphene nanocomposite as sodium ion battery negative electrode.
Detailed Description
The present invention is further analyzed with reference to the following detailed description.
Example 1 oxygen vacancy-containing SnO2Of graphene nanocompositesAnd (4) preparation.
A.SnO2-synthesis of graphene nanocomposites: 200mg of SnCl4·5H2Dissolving O in 15ml of pure water, and uniformly stirring; taking 10ml of graphene oxide aqueous solution with the concentration of 2mg/ml, and slowly dropwise adding the graphene oxide aqueous solution to SnCl4Placing the solution in an ultrasonic washing tank at the room temperature of 25 ℃ and shaking for 30min to obtain a yellow brown transparent clear solution. The obtained solution is packaged in a 50ml hydrothermal reaction kettle, heated to 160 ℃, and kept warm for 20 h. The solution after the hydrothermal treatment was centrifuged (7000rpm,10min), the supernatant was decanted and the resulting precipitate was dried in an oven under vacuum at 60 ℃ for 16 h.
B. Tempering treatment: the obtained dry powder was placed in an atmosphere-protected tube furnace and tempered at 600 ℃ while passing a gas containing 3 vol.% of H2H of (A) to (B)2The gas flow rate of the/Ar mixed gas was controlled at 100ml/min, and the treatment time was 3 hours, so as to introduce oxygen vacancy defects.
Comparative example, SnO free from oxygen vacancy defects2-preparation of graphene nanocomposites.
A.SnO2-synthesis of graphene nanocomposites: 200mg of SnCl4·5H2Dissolving O in 15ml of pure water, and uniformly stirring; taking 10ml of graphene oxide aqueous solution with the concentration of 2mg/ml, and slowly dropwise adding the graphene oxide aqueous solution to SnCl4Placing the solution in an ultrasonic washing tank at the room temperature of 25 ℃ and shaking for 30min to obtain a yellow brown transparent clear solution. The obtained solution is packaged in a 50ml hydrothermal reaction kettle, heated to 160 ℃, and kept warm for 20 h. The solution after the hydrothermal treatment was centrifuged (7000rpm,10min), the supernatant was decanted and the resulting precipitate was dried in an oven under vacuum at 60 ℃ for 16 h.
B. Tempering treatment: and placing the obtained dry powder in an atmosphere protection tube furnace, tempering at 600 ℃, introducing high-purity Ar gas, controlling the gas flow rate at 100ml/min, and treating for 3 hours.
It can be observed that the prepared oxygen-containing vacancy defect SnO2Graphene nanocomposites with typical graphene-based nanocomposite microstructure (fig. 1(a)), lamellar structureIs a graphene component, and the nano-particles are SnO2And (3) granules. Oxygen vacancy defect-containing SnO prepared in example 1 in comparison with comparative example (FIG. 1(b))2Graphene nanocomposites exhibit more wrinkles and holes in the micro-morphology, probably because graphene oxide is more fully reduced under a weakly reducing atmosphere, resulting in more oxygen-containing group valence bonds breaking. Oxygen vacancy defect SnO can be seen through TEM picture (figure 2) of sample2SnO of graphene nanocomposites2The grains exhibited rather fuzzy boundaries, as further observed by High Resolution Transmission Electron Microscopy (HRTEM), at SnO2The existence of a plurality of holes on the (110) crystal face proves that oxygen vacancy defects are introduced; while SnO of comparative example2The crystal grains show more obvious boundaries, the atoms on the crystal faces are arranged more orderly, and the defects are fewer. The X-ray diffraction (XRD) pattern (figure 3) of the tempered sample proves that SnO with oxygen vacancy defect is introduced2Still presents the typical red spar structure SnO2. Raman spectroscopy analysis (fig. 4) shows that tempering treatment in a reducing atmosphere has less effect on the graphene composition, only slightly changing the peak intensity ratio of the characteristic graphite peaks D and G (fig. 4 (a)); for SnO2Nanocrystalline component at 473cm after defect introduction-1A wave peak is formed at the position and is SnO2E of (A)gRaman active vibrational mode, evidencing the presence of oxygen vacancy defects. The valence state of the compound contained in the sample is analyzed by X-ray photoelectron spectroscopy (XPS) (FIG. 5), and the experimental result further proves that Sn in the sample has a valence state other than 4 (FIG. 5(b)), and graphene oxide has a valence state in H2More thorough reduction in the/Ar mixed atmosphere (FIG. 5(c)), and the presence of oxygen vacancy defects (FIG. 5 (d)). The above experimental conclusions are all consistent with each other, and the oxygen vacancy defect SnO is fully proved2Graphene nanocomposites were successfully prepared.
Application example 2 oxygen vacancy-containing SnO2-sodium storage performance testing of graphene nanocomposites
The oxygen-containing vacancy defect SnO prepared in example 12Graphene nanocomposites and control with S, respectivelyMixing the uperP carbon black and PVDF in a ratio of 75:15:10 wt.%, blending into paste by using an NMP solvent, coating the paste on the surface of a copper foil, and cutting the coated copper foil into a wafer with the diameter of 15mm after vacuum drying to be used as a sodium ion battery electrode. Electrolyte for sodium ion battery (EC: PC ═ 1:1, NaClO) is selected4Concentration of 1mol/L) and a metal sodium foil piece are used as counter electrodes, an RC2030 type button cell is assembled in a glove box, and a constant current charge and discharge test is carried out in a Newware BTS cell test system. The capacity test of the sodium ion battery adopts a constant current charge-discharge method for testing, the current density selected during the test is 40mA/g, the charge-discharge potential is from 0.05V to 3V, and the cycle is executed for 50 times. The multiplying power performance test is executed after 50 cycles, the selected current density is 40,100,240,600,1200mA/g, the charge-discharge potential is 0.05-3V, and each group of current density executes 10 cycles. The aging test of the sodium ion battery adopts a constant current charge and discharge method for testing, the current density selected during the test is 40mA/g, the charge and discharge potential is from 0.05V to 3V, and the cycle is executed for 300 times. As can be seen from FIGS. 7 and 8 in conjunction with FIG. 6, the material exhibited good sodium storage capacity (530mAh/g, current density 40mA/g), rate capability (391mAh/g, current density 1200mA/g) and cycle life (. gtoreq.500 mAh/g,300 cycles) when used as a negative electrode for a sodium ion battery, as compared to a comparative example that did not contain oxygen vacancy defects.
Example 2 oxygen vacancy-containing SnO2-preparation of graphene nanocomposites.
A.SnO2-synthesis of graphene nanocomposites: adding 100mg SnCl4·5H2Dissolving O in 15ml of pure water, and uniformly stirring; 5ml of graphene oxide aqueous solution with the concentration of 2mg/ml is taken and slowly dripped into SnCl4Placing the solution in an ultrasonic washing tank at the room temperature of 25 ℃ and shaking for 15min to obtain a yellow brown transparent clear solution. The obtained solution is packaged in a 50ml hydrothermal reaction kettle, heated to 140 ℃, and kept warm for 24 h. The solution after the hydrothermal treatment is centrifuged (5000rpm,10min), the supernatant liquid is decanted, and the obtained precipitate is placed in an oven and dried under vacuum at 80 ℃ for 12 h.
B. Tempering treatment: placing the obtained dry powder in an atmosphere protection tube furnace, and tempering at 400 DEG CWhile passing in H containing 8 vol.% of2H of (A) to (B)2The gas flow rate of the/Ar mixed gas is controlled to be 800ml/min, and the treatment time is 3 hours, so that oxygen vacancy defects are introduced.
Prepared SnO containing oxygen vacancy defects2The graphene nanocomposite material has a typical micro-morphology structure of the graphene nanocomposite material, similar to that of example 1, the lamellar structure is the graphene component, and the nanoparticles are SnO2And (3) granules. More folds and holes appear on the micro-morphology, and SnO is2There are many voids in the crystal plane of (a), demonstrating that oxygen vacancy defects are introduced.
When the material is used as a negative electrode of a sodium ion battery, the material shows good sodium storage capacity (480mAh/g, current density of 40mA/g), rate capability (324mAh/g, current density of 1200mA/g) and cycle life (more than or equal to 430mAh/g,300 cycles) compared with a comparative example without oxygen vacancy defects.
Example 3 oxygen vacancy-containing SnO2-preparation of graphene nanocomposites.
A.SnO2-synthesis of graphene nanocomposites: adding 300mg SnCl4·5H2Dissolving O in 15ml of pure water, and uniformly stirring; taking 8ml of graphene oxide aqueous solution with the concentration of 2mg/ml, and slowly dropwise adding the graphene oxide aqueous solution to SnCl4Placing the solution in an ultrasonic washing tank at the room temperature of 25 ℃ and shaking for 25min to obtain a yellow brown transparent clear solution. The obtained solution is packaged in a 50ml hydrothermal reaction kettle, heated to 150 ℃, and kept warm for 16 h. The solution after the hydrothermal treatment was centrifuged (6000rpm,6min), the supernatant was decanted and the resulting precipitate was dried in an oven under vacuum at 50 ℃ for 16 h.
B. Tempering treatment: the obtained dry powder was placed in an atmosphere-protected tube furnace and tempered at 500 ℃ while passing a gas containing 5 vol.% of H2H of (A) to (B)2The gas flow rate of the/Ar mixed gas was controlled at 50ml/min, and the treatment time was 5 hours, so as to introduce oxygen vacancy defects.
Prepared SnO containing oxygen vacancy defects2Graphene nanocomposites similar to example 1, with typical graphene-based nanocomposite micro-morphologyThe structure is that the lamellar structure is a graphene component, and the nano-particles are SnO2And (3) granules. More folds and holes appear on the micro-morphology, and SnO is2There are many voids in the crystal plane of (a), demonstrating that oxygen vacancy defects are introduced.
When the material is used as a negative electrode of a sodium ion battery, the material shows good sodium storage capacity (473mAh/g and 40mA/g current density) and rate capability (311mAh/g and 1200mA/g current density) and cycle life (427 mAh/g and 300 cycles) compared with a comparative example without oxygen vacancy defects.
In conclusion, the above-mentioned application of sodium battery is only the preferred embodiment of the present invention, and all the equivalent changes and modifications made in the claims of the present invention shall fall within the scope of the present invention.
Claims (4)
1. SnO containing oxygen vacancy defects2-a graphene nanocomposite material, prepared by the following method steps, characterized in that:
step (1), slowly dropwise adding the graphene oxide aqueous solution to SnCl4In solution at 25oC, placing the mixture in an ultrasonic washing tank at room temperature and oscillating for 15-30 min to obtain a yellow brown transparent clear solution;
step (2), packaging the solution obtained in step (1) in a 50ml hydrothermal reaction kettle, heating to 140-oC, preserving heat for 16-24 hours;
and (3) carrying out centrifugal separation on the solution treated in the step (2), pouring out supernatant clear liquid, placing the obtained precipitate in an oven, and carrying out 50-80% concentrationoC, vacuum drying for 12-16 h;
step (4), placing the dry powder obtained in step (3) in an atmosphere protection tube furnace at 400-oTempering treatment is carried out under C, reducing gas is introduced at the same time, the gas flow rate is controlled to be 50-800 ml/min, the treatment time is 3-5 hours, and the needed oxygen-containing vacancy defect SnO is obtained2-a graphene nanocomposite; wherein the reducing gas is introduced to contain 3-8 vol.% H2H of (A) to (B)2and/Ar mixed gas.
2. An SnO having oxygen vacancy defects as defined in claim 12-graphene nanocomposites characterized by graphene oxide with SnCl4The mass ratio of (10-20) to (74.3-222.9).
3. An SnO having oxygen vacancy defects as defined in claim 12The graphene nanocomposite is characterized in that the centrifugation condition in the step (3) is 5000-7000 rpm, and the centrifugation time is 5-10 min.
4. An SnO having oxygen vacancy defects as defined in claim 12Application of the graphene nanocomposite to a cathode of a normal-temperature sodium-ion battery.
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