CN109301187A - Carbon coating SnO applied to negative electrode of lithium ion batteryxQuantum dot/graphene complex preparation method - Google Patents

Carbon coating SnO applied to negative electrode of lithium ion batteryxQuantum dot/graphene complex preparation method Download PDF

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CN109301187A
CN109301187A CN201811056972.7A CN201811056972A CN109301187A CN 109301187 A CN109301187 A CN 109301187A CN 201811056972 A CN201811056972 A CN 201811056972A CN 109301187 A CN109301187 A CN 109301187A
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CN109301187B (en
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胡毅
沈桢
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Zhejiang Sci Tech University ZSTU
Zhejiang University of Science and Technology ZUST
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/364Composites as mixtures
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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Abstract

A kind of carbon coating SnO applied to negative electrode of lithium ion battery of the present inventionxQuantum dot/graphene complex preparation method.Method includes the following steps: the configuration of (1) solution to be irradiated: (2) irradiation: the resulting solution to be irradiated of step (1) being placed under excimer light source and is irradiated, is stirred simultaneously;(3) carbon coating SnOxQuantum dot/graphene complex preparation: by step (2) product obtained in H2It is calcined in/Ar gaseous mixture atmosphere, carbon coating SnO is madexQuantum dot/graphene complex.Preparation method of the present invention is simple, process is short, high-efficient.Carbon coating layer not only effectively disperses SnOxQuantum dot, and can be used as SnOxThe volume change generated in charge and discharge process plays inhibiting effect, can also accelerate electronics in SnOxThe migration on quantum dot surface layer.This carbon coating SnOxQuantum dot/graphene complex can be used as the negative electrode material of lithium ion battery, sodium-ion battery.

Description

Carbon coating SnO applied to negative electrode of lithium ion batteryxQuantum dot/graphene complex Preparation method
Technical field
The present invention relates to energy storage system device material field, in particular to a kind of carbon packet applied to negative electrode of lithium ion battery Cover SnOxQuantum dot/graphene complex preparation method.
Background technique
21 century improves with social production development and economic life, and environment and energy problem are increasingly prominent.The mankind are to new The craving of the energy is more more and more urgent, and finding the green sustainable energy of exploitation and energy technology already becomes the research heat of the world today Point.The exploitation of the energy and the research of energy technology necessarily involve energy conversion and energy storage.The mankind are to renewable energy at present The development and utilization level in source is advanced by leaps and bounds, however it is obvious intermittent further to utilize solar energy, wind energy, tide energy etc. to have Renewable energy, it is necessary to be equipped with suitable high efficiency energy memory device.Electrochmical power source is convert chemical energy to electric energy new Type high efficient energy sources technology device has obtained extensive research and swift and violent development in recent decades.And the chemistry of recyclable work Power supply, i.e. secondary cell, more meet the needs of people are growing.Currently, secondary cell in the market mainly have lead-acid battery, Nickel-cadmium cell, nickel-metal hydride battery and lithium ion battery.
Lithium ion battery has many advantages, such as that operating voltage is high, energy density is big, has extended cycle life, is environment friendly and pollution-free, as High efficiency energy memory device is widely applied in production and living.Negative electrode material is the key element for determining performance of lithium ion battery One of.The cathode having been commercialized at present is mostly the carbon-based material of high electrochemical stability, but its lower theoretical capacity (such as: Graphite is 372mAh/g) it is unable to reach the high capacity usability requirement of energy storage device.
Content of the tin on the earth's crust is high, abundance, and tin-based material theoretical capacity with higher, and simple substance tin theory is held Amount is 990mAh/g, and stannic oxide (SnO2) theoretical capacity be 1494mAh/g.But in charge and discharge process, with lithium ion Intercalation/deintercalation, SnO2Volume expansion/contraction that nearly 300% can be generated causes its dusting fragmentation to fall off, and on the one hand influences activity Electrical contact between substance and collector, is unfavorable for electron-transport, and battery capacity is made to decay rapidly;On the other hand make active matter The solid electrolyte film (SEI) formed between matter and electrolyte constantly thickeies, and declines the cycle performance of battery sharply.
It solves the above problems there are many approach, the following can be summarized as: (1) introducing backing material (such as carbon material, metal Oxide), with SnO2Mixing embedding contain or coats;(2) reduce SnO2Particle size, to reduce bulk effect;(3) design synthesis Stable SnO2Space geometry structure (such as: hollow sphere, hollow cube).Thus a large amount of novel SnO are constructed2Sill, Such as zero-dimension nano particle, one-dimensional nano line, two-dimensional nano piece etc..Wherein zero-dimension nano particle is because of its isotropic sphere knot Structure and have best mechanical stability.But the large specific surface area of nano particle, surface can be high, easy to reunite, and electrical contact is caused to be dropped It is low, especially for smaller SnO2Quantum dot is reunited very serious.
Graphene has biggish specific surface area due to its unique two-dimensional structure, by SnO2Quantum dot is deposited on graphite On alkene, SnO can be prevented2The reunion of quantum dot.Moreover, the high conduction performance of graphene greatly promotes SnO2Quantum dot surface Electron transfer rate, to improve its chemical property.SnO as a result,2Quantum dot/graphene complex can be used as lithium-ion electric One of the ideal material of pond cathode.At present, it has been reported that a variety of preparation SnO2Quantum dot/graphene complex method.Such as CN107055516A discloses to report to be reacted 5-120 minutes using microwave hydrothermal, and temperature is 120-180 DEG C, resulting SnO2Amount Tin dioxide quantal-point size uniformity in sub- point/graphene complex, and it is evenly distributed on the two sides of graphene film; CN105895874A, which is disclosed, to be reported using multiple ball milling, preprocessed and high-temperature calcination, most obtains SnO through filtering afterwards2Quantum Point/graphene complex;CN103441254A, which discloses to report using urea, is flowed back 16 as reducing agent under the conditions of 85-90 DEG C Hour, 2 hours reduction-oxidation graphite is calcined at high temperature, and SnO is made2Quantum dot/graphene complex.Although these methods exist SnO can be improved in varying degrees2Deposition effect of the quantum dot on graphene, but still it is unable to reach an ultra-uniform dispersed State.Still further aspect, SnOxIt can get because surface has oxygen vacancies abundant and compare SnO2Higher capacity, since oxygen vacancies can Increase additional fake capacitance effect.But in currently reported, SnOxThe preparation of quantum dot and SnO2Quantum dot faces similarly Problem.
Excimer UV light irradiation technique has the characteristics that Simple energy-saving, green high-efficient, and operating condition is controllably extremely suitable Large area processing is closed, is widely applied in fields such as hygiene medical treatment, food processings.The irradiation of Excimer UV light is used for Nano carbon fibers Tie up film surface processing and as lithium ion battery negative material it has been reported that but as assisted deposition technique, be applied to SnOxQuantum dot/graphene complex preparation method has not been reported.
Summary of the invention
The present invention provides a kind of easy, efficient SnO for being applied to negative electrode of lithium ion batteryxQuantum dot/graphene is compound The preparation method of object.
The technical solution used to solve the technical problems of the present invention is that:
A kind of carbon coating SnO applied to negative electrode of lithium ion batteryxQuantum dot/graphene complex preparation method, should Method the following steps are included:
(1) configuration of solution to be irradiated: a. graphene is mixed with deionized water, and ultrasound mixes;B. sucrose is taken to be substantially soluble in In dilute hydrochloric acid, stannous chloride is added;C. two kinds of mixed liquors that step a and step b are obtained are to be irradiated through being mixed evenly to obtain Solution;The mass fraction of graphene is 0.08-0.4% in solution to be irradiated, and the mass fraction of sucrose is 2-15%, stannous chloride Mass fraction be 5-20%, dilute hydrochloric acid concentration be 1-3%;
(2) it irradiates: the resulting solution to be irradiated of step (1) being placed under excimer light source and is irradiated, is stirred simultaneously;
(3) carbon coating SnOxQuantum dot/graphene complex preparation: by step (2) product obtained in H2/ Ar mixing Atmosphere encloses middle calcining, and carbon coating SnO is madexQuantum dot/graphene complex.
Preparation method of the present invention is simple, process is short, high-efficient.SnOxQuantum dot can provide high lithium storage content;Carbon coating layer Not only effectively dispersion SnOxQuantum dot, and can be used as SnOxThe volume change generated in charge and discharge process plays inhibiting effect, may be used also Accelerate electronics in SnOxThe migration on quantum dot surface layer.This carbon coating SnOxQuantum dot/graphene complex can be used as lithium-ion electric Pond, sodium-ion battery negative electrode material.
Preferably, in the step (1), mixing time 2-10min.
Preferably, the mass fraction of graphene is 0.15-0.35%, sucrose in solution to be irradiated in the step (1) Mass fraction be 5-12%, the mass fraction of stannous chloride is 5-15%, and dilute hydrochloric acid concentration is 1.5-2%.When mixing Between 4-7min.
Graphene content is too low, be easy to cause deposition irregular, excessively high, is not easy ultrasonic disperse;Cane sugar content is too low, cladding Effect is unobvious, excessively high, can reduce final SnOxThe relative amount of quantum dot, to reduce the specific capacity of cathode;Stannous chloride Content is too low, and it is insufficient to will cause deposition, so that the specific capacity of cathode is reduced, it is excessively high irregular it will cause depositing;Dilute hydrochloric acid rises The effect not oxidized to protection stannous chloride, process effect is unobvious, while dilute hydrochloric acid can also dissolve the SnO of part formationx Quantum dot, therefore too high levels can then reduce SnOxThe relative amount of quantum dot, to reduce the specific capacity of cathode.
Preferably, the excimer light source is KrCl*、XeCl*Or Xe2 *, optimal selection KrCl.
XeCl*Excimer UV lamp wavelength is 308nm, and as assistant depositing light source, the energy provided is not high enough, therefore is imitated Rate is lower;Xe2 *Molecule ultraviolet lamp wavelength is 172nm, and under the illumination of this wavelength, the oxygen in air can be converted into ozone, mistake Amount is then harmful to the human body, therefore higher to the environmental requirement of irradiation;KrCl*Excimer UV lamp wavelength is 222nm, relatively mild And efficiently, it is suitble to apply in open environment, it is lower to ambient enviroment and supplemental equipment requirement.
Preferably, in the step (2), irradiation distance 0.2-1cm, irradiation time 1-60min, speed of agitator 50-200 Rev/min.Further, in the step (2), irradiation distance 0.3-0.7cm, irradiation time 10-40min, speed of agitator 10- 150 revs/min.Distance is too short, is difficult to control, too long ineffective;Time too short low efficiency, it is too long to equipment damage;Stirring It is too slow, easily graphene is caused to precipitate, causes SnOxQuantum spot deposition is irregular, too fastly then cause to irradiate it is insufficient, influence deposit matter Amount.
Preferably, in the step (3), H2/ Ar mixed gas flow is 50-500sccm, calcination temperature 300-500 DEG C, time 0.5-3h.Flow, calcination temperature, time value are too small, and effect is unobvious, too big then easily to form simple substance tin, 400 Melting is agglomerated into bulky grain at DEG C.
The present invention is the carbon coating SnO applied to negative electrode of lithium ion batteryxQuantum dot/graphene complex preparation side Method prepares the solution of the dispersion liquid and sucrose of graphene and deionized water, stannous chloride, dilute hydrochloric acid respectively first;It is uniformly mixed The irradiation of Excimer UV light is carried out afterwards;Carbon coating SnO is obtained through high-temperature calcination againxQuantum dot/graphene complex.Party's legal system Standby carbon coating SnOxQuantum dot/graphene complex can be used for lithium ion battery energy storage field.This preparation method has as follows Feature:
(1) preparation method of the present invention is easy, and process is short, high-efficient, and radiation parameter is easy to accomplish and controls.
(2) carbon coating layer prepared by, uniform fold is in SnOxOn quantum dot, SnO both can inhibitxQuantum dot is in electrochemistry Bulk effect in the process can also be SnOxQuantum dot provides quick electron propagation ducts, to improve SnOxQuantum dot/stone The cyclical stability and high rate performance of black alkene cathode composite.
(3) SnO prepared byxQuantum dot, by carbon coating layer isolation, high degree of dispersion is deposited on graphene, is strengthened every A SnOxContact of the quantum dot with graphene enhances carbon coating SnO to provide efficient electrochemical reaction conditionxQuantum Point/graphene complex cathode high rate performance.
(4) SnO prepared byxQuantum dot, oxygen vacancies rich in, therefore there is fake capacitance effect, it can greatly improve Carbon coating SnOxQuantum dot/graphene complex cathode rate capability.
Detailed description of the invention
Fig. 1 is carbon coating SnO obtained by embodiment 1xQuantum dot/graphene complex TEM transmission electron microscope picture.
Fig. 2 is carbon coating SnO obtained by embodiment 1xQuantum dot/graphene complex high-resolution TEM transmission electron microscope picture.
Fig. 3 is SnO obtained by embodiment 2xQuantum dot/graphene complex TEM transmission electron microscope picture.
Fig. 4 is carbon coating SnO obtained by embodiment 3xQuantum dot/graphene complex TEM transmission electron microscope picture.
Fig. 5 is carbon coating SnO obtained by embodiment 4xQuantum dot/graphene complex TEM transmission electron microscope picture.
Fig. 6 is carbon coating SnO obtained by embodiment 5xQuantum dot/graphene complex TEM transmission electron microscope picture.
Fig. 7 is SnO obtained by embodiment 62Quantum dot/graphene complex high-resolution TEM transmission electron microscope picture.
Fig. 8 is carbon coating SnO obtained by embodiment 1xCarbon obtained by quantum dot/graphene complex and embodiment 6 Coat SnO2Quantum dot/graphene complex ESR ESR spectrum figure.
Fig. 9 is carbon coating SnO obtained by embodiment 1xQuantum dot/graphene complex, 6 carbon coating SnO of embodiment2Amount The high rate performance figure of sub- point/graphene complex.
Specific embodiment
Below by specific embodiment, technical scheme of the present invention will be further explained in detail.It should be appreciated that this hair Bright implementation is not limited by the following examples, and the accommodation in any form made to the present invention and/or changed will all be fallen Enter the scope of the present invention.
In the present invention, if not refering in particular to, all parts, percentage are unit of weight, and all equipment and raw material etc. are equal It is commercially available or the industry is common.
Embodiment 1
A kind of carbon coating SnO applied to negative electrode of lithium ion batteryxQuantum dot/graphene complex preparation method, should Method and step is as follows:
(1) accurately claim 60mg graphene powder with assay balance, ultrasonic disperse is in 10mL deionized water;Separately weigh 2g sugarcane Sugar is dissolved in the dilute hydrochloric acid of 10mL 1.8%, adds 1.6g stannous chloride dihydrate powder, after completely dissolution, with graphene Aqueous dispersions are mixed 5 minutes, obtain the solution to be irradiated of stable homogeneous.
(2) it irradiates: solution to be irradiated is placed in KrCl*It stirs and irradiates, irradiation time at 0.5cm under excimer light source 20min, 50 revs/min of speed of agitator.
(3) by after the mixed liquor clean dry after irradiation, in H2It is calcined in/Ar gaseous mixture atmosphere, controls H2/ Ar gaseous mixture Flow is 50sccm, and calcination temperature is 400 DEG C, time 1h, and carbon coating SnO is madexQuantum dot/graphene complex.
Embodiment 2
A kind of carbon coating SnO applied to negative electrode of lithium ion batteryxQuantum dot/graphene complex preparation method, should Method and step is as follows:
(1) accurately claim 60mg graphene powder with assay balance, ultrasonic disperse is in 10mL deionized water;Separately weigh 1.6g Stannous chloride dihydrate powder is substantially soluble in the dilute hydrochloric acid of 10mL 1.8%, is mixed 5 points with the aqueous dispersions of graphene Clock.
(2) it irradiates: solution to be irradiated is placed in KrCl*It stirs and irradiates, irradiation time at 0.5cm under excimer light source 20min, 50 revs/min of speed of agitator.
(3) by after the mixed liquor clean dry after irradiation, in H2It is calcined in/Ar gaseous mixture atmosphere, controls H2/ Ar gaseous mixture Flow is 50sccm, and calcination temperature is 400 DEG C, time 1h, and carbon coating SnO is madexQuantum dot/graphene complex.
Embodiment 3
A kind of carbon coating SnO applied to negative electrode of lithium ion batteryxQuantum dot/graphene complex preparation method, should Method and step is as follows:
(1) accurately claim 60mg graphene powder with assay balance, ultrasonic disperse is in 10mL deionized water;Separately weigh 2g sugarcane Sugar is dissolved in the dilute hydrochloric acid of 10mL 1.8%, adds 1.6g stannous chloride dihydrate powder, after completely dissolution, with graphene Aqueous dispersions are mixed 5 minutes, obtain the solution to be irradiated of stable homogeneous.
(2) mixed liquor in (1) is stirred into 20min with 50 revs/min of speed of agitator.
(3) by after the mixed liquor clean dry obtained in (2), in H2It is calcined in/Ar gaseous mixture atmosphere, controls H2/ Ar mixing Throughput is 50sccm, and calcination temperature is 400 DEG C, time 1h, and carbon coating SnO is madexQuantum dot/graphene complex.
Embodiment 4
A kind of carbon coating SnO applied to negative electrode of lithium ion batteryxQuantum dot/graphene complex preparation method, should Method and step is as follows:
(1) accurately claim 60mg graphene powder with assay balance, ultrasonic disperse is in 10mL deionized water;Separately weigh 2g sugarcane Sugar is dissolved in the dilute hydrochloric acid of 10mL 1.8%, adds 1.6g stannous chloride dihydrate powder, after completely dissolution, with graphene Aqueous dispersions are mixed 5 minutes, obtain the solution to be irradiated of stable homogeneous.
(2) it irradiates: solution to be irradiated is placed in KrCl*It stirs and irradiates, irradiation time at 0.5cm under excimer light source 10min, 50 revs/min of speed of agitator.
(3) by after the mixed liquor clean dry after irradiation, in H2It is calcined in/Ar gaseous mixture atmosphere, controls H2/ Ar gaseous mixture Flow is 50sccm, and calcination temperature is 400 DEG C, time 1h, and carbon coating SnO is madexQuantum dot/graphene complex.
Embodiment 5
A kind of carbon coating SnO applied to negative electrode of lithium ion batteryxQuantum dot/graphene complex preparation method, should Method and step is as follows:
(1) accurately claim 60mg graphene powder with assay balance, ultrasonic disperse is in 10mL deionized water;Separately weigh 2g sugarcane Sugar is dissolved in the dilute hydrochloric acid of 10mL 1.8%, adds 1.6g stannous chloride dihydrate powder, after completely dissolution, with graphene Aqueous dispersions are mixed 5 minutes, obtain the solution to be irradiated of stable homogeneous.
(2) it irradiates: solution to be irradiated is placed in KrCl*It stirs and irradiates, irradiation time at 0.5cm under excimer light source 30min, 50 revs/min of speed of agitator.
(3) by after the mixed liquor clean dry after irradiation, in H2It is calcined in/Ar gaseous mixture atmosphere, controls H2/ Ar gaseous mixture Flow is 50sccm, and calcination temperature is 400 DEG C, time 1h, and carbon coating SnO is madexQuantum dot/graphene complex.
Embodiment 6
A kind of carbon coating SnO applied to negative electrode of lithium ion batteryxQuantum dot/graphene complex preparation method, should Method and step is as follows:
(1) accurately claim 60mg graphene powder with assay balance, ultrasonic disperse is in 10mL deionized water;Separately weigh 2g sugarcane Sugar is dissolved in the dilute hydrochloric acid of 10mL 1.8%, adds 1.6g stannous chloride dihydrate powder, after completely dissolution, with graphene Aqueous dispersions are mixed 5 minutes, obtain the solution to be irradiated of stable homogeneous.
(2) it irradiates: solution to be irradiated is placed in KrCl*It stirs and irradiates, irradiation time at 0.5cm under excimer light source 20min, 50 revs/min of speed of agitator.
(3) it by after the mixed liquor clean dry after irradiation, is calcined in Ar gaseous mixture atmosphere, control Ar mixed gas flow is 50sccm, calcination temperature are 400 DEG C, time 1h, and carbon coating SnO is made2Quantum dot/graphene complex.
Three variable comparative examples have been done by this seminar: adding sucrose in 1. raw materials and sucrose (embodiment 1,2) is not added;2. Irradiation time 0,10,20,30min (embodiment 3,4,1,5);3. logical H when calcining2/ Ar and pure Ar (embodiment 1,6), according to reality Interpretation of result is tested, is obtained as drawn a conclusion:
It is found by the TEM transmission electron microscope observing of Fig. 1 and Fig. 3, sucrose, the carbon packet of acquisition embodiment 1: is added in the feed Cover SnOxIn quantum dot/graphene complex, carbon coating SnOxDispersibility of the quantum dot on graphene adds significantly better than no sucrose The SnO addedxQuantum dot/graphene complex.
It is found by the TEM transmission electron microscope observing of Fig. 1, Fig. 4, Fig. 5 and Fig. 6, with the extension of irradiation time, carbon coating SnOxDeposition of the quantum dot on graphene gradually increases;When irradiation time is 20min and 30min, carbon coating SnOxQuantum dot is heavy Accumulated amount variation it is unobvious, illustrate irradiation time in 20min, carbon coating SnOxQuantum dot reaches optimal deposition on graphene Amount.
It is found by the high-resolution TEM transmission electron microscope observing of Fig. 2 and Fig. 7, in H2High-temperature calcination under/Ar mixed atmosphere, can Obtain carbon coating SnOxQuantum dot, and under pure Ar atmosphere, acquisition is carbon coating SnO2Quantum dot.
It can be obtained by the electron paramagnetic resonance spectrum analysis of Fig. 8, in H2The SnO calcined in/Ar mixed atmospherexQuantum Point has oxygen vacancies, further proves carbon coating SnOxThe presence of quantum dot.
It is to carbon coating SnO hereinxQuantum dot/graphene complex fundamental property description, about similar product performance Comparison hereafter given and described.
By carbon coating SnO obtained in embodiment 1xQuantum dot/graphene complex as negative electrode of lithium ion battery, into Row electro-chemical test, high rate performance figure are as shown in Figure 9.As seen from Figure 9, carbon coating SnOxQuantum dot/graphene is compound Object negative battery and carbon coating SnO2Quantum dot/graphene complex negative battery initial discharge capacity is almost consistent;It will be electric When current density is gradually risen by 0.05A/g to 3.2A/g, carbon coating SnOxQuantum dot/graphene complex negative battery is shown Apparent capacity advantage;After current density turns again to 0.05A/g, carbon coating SnOxQuantum dot/graphene complex cathode Battery capacity with higher.Test result shows the carbon coating SnO prepared in embodiment 1xQuantum dot/graphene complex is negative Pole battery shows optimal high rate performance.
Above-mentioned embodiment is only a preferred solution of the present invention, not the present invention is made in any form Limitation, there are also other variations and modifications on the premise of not exceeding the technical scheme recorded in the claims.

Claims (7)

1. a kind of carbon coating SnO applied to negative electrode of lithium ion batteryxQuantum dot/graphene complex preparation method, feature Be method includes the following steps:
(1) configuration of solution to be irradiated: a. graphene is mixed with deionized water, and ultrasound mixes;B. sucrose is taken to be substantially soluble in dilute salt In acid, stannous chloride is added;C. two kinds of mixed liquors that step a and step b are obtained are through being mixed evenly to obtain solution to be irradiated; The mass fraction of graphene is 0.08 0.4% in solution to be irradiated, and the mass fraction of sucrose is 2 15%, the quality of stannous chloride Score is 5 20%, and dilute hydrochloric acid concentration is 1 3%;
(2) it irradiates: the resulting solution to be irradiated of step (1) being placed under excimer light source and is irradiated, is stirred simultaneously;
(3) carbon coating SnOxQuantum dot/graphene complex preparation: by step (2) product obtained in H2/ Ar mixed atmosphere Middle calcining is enclosed, carbon coating SnO is madexQuantum dot/graphene complex.
2. preparation method according to claim 1, it is characterised in that: in the step (1), mixing time 2 10 min。
3. preparation method according to claim 1, it is characterised in that: in the step (1), in the step (1), to spoke Mass fraction according to graphene in solution is 0.15 0.35%, and the mass fraction of sucrose is 5 12%, the mass fraction of stannous chloride It is 5 15%, dilute hydrochloric acid concentration is 1.5 2%.
4. preparation method according to claim 1, it is characterised in that: the excimer light source is KrCl*、XeCl*Or Xe2 *
5. preparation method according to claim 1, it is characterised in that: in the step (2), 0.2 1 cm of irradiation distance, 1 60 min of irradiation time, 50 200 revs/min of speed of agitator.
6. preparation method according to claim 1, it is characterised in that: in the step (2), irradiation distance 0.3 0.7 Cm, 10 40 min of irradiation time, 10 150 revs/min of speed of agitator.
7. preparation method according to claim 1, it is characterised in that: in the step (3), H2/ Ar mixed gas flow is 50 500 sccm, calcination temperature are 300 500 DEG C, and the time is 0.5 3 h.
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