CN108598405A - A kind of preparation method of three-dimensional grapheme tin oxide carbon compound cathode materials - Google Patents

A kind of preparation method of three-dimensional grapheme tin oxide carbon compound cathode materials Download PDF

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CN108598405A
CN108598405A CN201810341294.2A CN201810341294A CN108598405A CN 108598405 A CN108598405 A CN 108598405A CN 201810341294 A CN201810341294 A CN 201810341294A CN 108598405 A CN108598405 A CN 108598405A
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tin oxide
graphene
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dimensional grapheme
cathode materials
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CN108598405B (en
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武大鹏
任好雨
杨东晓
王红菊
徐芳
高志永
蒋凯
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Henan Normal University
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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
    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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 kind of preparation methods of three-dimensional grapheme tin oxide carbon compound cathode materials, belong to the synthesis technical field of inorganic functional material.Technical scheme of the present invention main points are：Three-dimensional grapheme tin oxide carbon compound cathode materials, which are the stannum oxide nano-crystal uniform loads by size uniformity, to carry out in three-dimensional grapheme reticular structure, and using Dopamine hydrochloride as nitrogen source and carbon source made from a step N doping and carbon coating.The present invention effectively alleviates the volume expansion that tin oxide occurs during alloying and de- alloy, enhances the stability of lithium ion battery negative material.

Description

A kind of preparation method of three-dimensional grapheme tin oxide carbon compound cathode materials
Technical field
The invention belongs to the synthesis technical fields of inorganic functional material, and in particular to a kind of three-dimensional grapheme tin oxide carbon is multiple Close the preparation method of negative material.
Background technology
Lithium ion battery with high-energy density and good circulation performance is widely used in mancarried electronic aid and energy Source storage facilities, although input application, lower theoretical specific capacity seriously limit carbon-based negative material on a large scale The industrialization of lithium ion battery is made.Graphene has been used as lithium ion battery negative material 20 years, due to the reason of graphene It is 372 mAh h by capacity-1, and performance is poor in the case of high rate charge-discharge.Due to its own low cost, environmental protection and Higher theoretical specific capacity, SnO2Become a kind of more promising alternative materials.Importantly, with other transition metal Oxide is compared, SnO2With lower operating voltage（Platform discharge voltage is between 0.3-0.5 V）, so as to cause SnO2 There is higher energy density in lithium ion battery negative material application aspect.Therefore, seek a kind of high power capacity and good circulation The electrode material of performance becomes an extremely urgent task.In addition, tin oxide is also abundant, environment-protecting and non-poisonous etc. excellent with produce Point.Therefore, tin oxide has become a hot spot studied as lithium ion battery anode material in recent years.SnO2Electric discharge Journey can be illustrated with following equation：
SnO2 + 4 Li+ + 4e- → Sn + 2 Li2O （1）
Sn + x Li+ + x e-↔ LixSn (0 ≤ x ≤ 4.4) （2）
For simple SnO2Material, first reaction process are irreversible, and theoretical capacity only has 780 mAh g-1.And for The SnO of nanosizing2, first reaction process is then that reversible or part is reversible, and theoretical capacity reaches 1494 mAh g-1, This capacity has reached 3 times of business graphite capacity.Second reaction is then one and is widely believed that reversible reaction, that is, exists Generation alloying that can be repeatedly during charge and discharge and the reaction of de- alloy.Improving, lithium ion battery negative material cycle is steady Qualitative aspect, SnO2The violent volume expansion occurred during charge and discharge（>300%）An always barrier for being difficult to overcome Hinder.In order to improve the cyclical stability of lithium ion battery, vast researcher is by the different pattern of tin oxide to battery performance Influence studied, for example, nano wire, nanotube, nanometer sheet, solid and hollow Nano microballoon etc..Carry high performance side For method other than it can be controlled by pattern, element doping is also a kind of very common mode, such as graphene and tin oxide Compound, tin oxide and titanium oxide are compound, and still, this problem is not well solved in research work before. Therefore, the stability of raising oxidation tin negative pole material is still a problem urgently to be resolved hurrily.
Publication No. CN 105742635A's specially uses glucose as carbon source and has synthesized carbon-coated graphene tin oxide Compound, in 100 mA g-1Current density under after 100 charge and discharge cycles discharge capacity be maintained at 750 mAh g-1.The patent of Publication No. CN 106159245A uses hydrazine hydrate or sodium borohydride to aoxidize tin composite to graphene as reducing agent It is restored, graphene oxidation tin composite has been obtained, in 100 mA g-1Current density under pass through 100 charge and discharge Discharge capacity is maintained at 820 mAh g after cycle-1.The patent of Publication No. CN 105355891A is by graphene and polystyrene Compound particle film is obtained after compound, compound particle film is then carried out high temperature with tin oxide presoma by way of calcining forges Burn, obtained tin oxide base composite material, under the current density of 0.3 C after 100 charge and discharge cycles discharge capacity It is maintained at 850 mAh g-1.Therefore, tin oxide above needs to be further increased in the application of energy storage material.
Invention content
The technical problem to be solved by the present invention is to provide a kind of simple for process and low-cost three-dimensional grapheme tin oxide The preparation method of carbon compound cathode materials, composite negative pole material made from this method is using graphene as structural unit, by graphene Nanocrystalline successfully In-situ reaction is in graphene network structure, and then by the high ratio of the satisfactory electrical conductivity of graphene and tin oxide Capacity organically combines, and introducing lone pair electrons finally by N doping increases active site, and carbon coating further reduces oxygen Change the volume change that tin occurs in charge and discharge process, effectively alleviates tin oxide and sent out during alloying and de- alloy Raw volume expansion enhances the stability of lithium ion battery negative material.
The present invention adopts the following technical scheme that solve above-mentioned technical problem, a kind of three-dimensional grapheme tin oxide carbon Compound Negative The preparation method of pole material, it is characterised in that the specific steps are：The 6.4 mL gels for containing 0.128 g graphene oxides are added Into beaker, takes n-butanol to be added to and make that the total volume of solution is 32 mL in beaker, 0.6 mL concentrated hydrochloric acids are then added, stir 10 min are mixed, by 0.6mmol SnCl under stirring condition2·2 H2O is added in beaker, and 40 min of ultrasound wait for that graphene solution is complete After full dispersion, suspension obtained is transferred in hydrothermal reaction kettle and in 180 DEG C of 2 h of hydro-thermal reaction, waits for that hydrothermal reaction kettle is cold But it to after room temperature, the sediment alcohol of gained is washed and washed obtains graphene for 3 times and aoxidizes tin composite, then by graphene tin oxide Compound is added in the Tris solution of 10 mM, stirs 10 min, and 0.15 g Dopamine hydrochlorides are added, 6 h are stirred under room temperature, It is washed 3 times with deionized water and ethyl alcohol after solution is centrifuged, by product in -80 DEG C of 10 h of precooling, it is dry to be then transferred to freezing 48 h are lyophilized in dry machine, then product is warming up to 550 DEG C of 3 h of calcining with the heating rate of 5 DEG C/min in nitrogen atmosphere and is made Dopamine hydrochloride carbonization is coated, the carbon-coated graphene tin oxide composite negative pole material of N doping is finally obtained.
Further preferably, the three-dimensional grapheme tin oxide carbon compound cathode materials are the oxidation sijnas by size uniformity The brilliant uniform load of rice carries out a step N doping in three-dimensional grapheme reticular structure, and using Dopamine hydrochloride as nitrogen source and carbon source Made from carbon coating, wherein the size of stannum oxide nano-crystal is 8-18 nm.
The present invention has the advantages that compared with prior art：The present invention passes through tune in the acidic environment of concentrated hydrochloric acid The ratio of graphene and tin oxide is saved to adjust the reversible capacity of negative material.It compared not mixing using the difference of carbon source simultaneously Miscellaneous hetero atom and the performance after nitrogen was adulterated, to obtain a kind of there is height ratio capacity and the good stone of cyclical stability Black alkene tin oxide carbon compound cathode materials.This method preparation method is simple, and repetitive rate is high, obtained three-dimensional grapheme tin oxide Carbon compound cathode materials have higher high rate performance and cyclical stability.
Description of the drawings
Fig. 1 is pure SnO2（A, b）And graphene oxide（C, d）SEM figure；
Fig. 2 is sample 3DG@SnO2The SEM of@N-C-2（a-e）、TEM（e）And Mapping（f-i）Analysis chart；
Fig. 3 is sample 3DG@SnO2The XRD analysis figure of@N-C-2；
Fig. 4 is sample 3DG@SnO2@N-C-2 are in 100 mA g-1Current density under charge and discharge cycles test chart；
Fig. 5 is sample 3DG@SnO2@N-C-2 are in 200 mA g-1Cycle performance test chart under current density；
Fig. 6 is sample 3DG@SnO2High rate performance test charts of the@N-C-2 under different current densities.
Specific implementation mode
The above of the present invention is described in further details by the following examples, but this should not be interpreted as to this The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on the above of the present invention belong to this hair Bright range.
Embodiment
Graphene oxide is obtained by Hummer ' the s legal systems for improveing classical（20 mg mL-1）.By improveing classics Hummer ' s legal systems obtain graphene oxide：The round-bottomed flask of 250 mL is taken, the 46 mL concentrated sulfuric acids is weighed and 0.1 g KNO is added3, NO is introduced during this3 -Ion enhances the strong oxidizing property of concentrated acid to a certain extent.10 min are stirred to wait being completely dissolved Afterwards, 2 g graphite are weighed, are slowly added into flask under stirring condition, about 1 h of used time, after continue to stir 10 min, with true Protect graphite more complete stripping in concentrated sulfuric acid.6 g potassium permanganate are weighed, are slowly added into flask under the conditions of ice bath stirring, About 1 h of used time, meeting heat release, is slowly added to be provided to prevent with ice-water bath quick-fried during potassium permanganate is added It is fried.Continue to stir 2 h under the conditions of ice-water bath so that graphite is more completely peeling-off in the solution of strong acid and is aoxidized. During this, the color of the mixture solution of the concentrated sulfuric acid, graphite and potassium permanganate gradually becomes blackish green from black, illustrates stone Oxidation reaction has occurred in ink in this process.Flask is transferred in 35 DEG C of oil bath and continues to stir 1 h, is then shifted again Into ice-water bath, 92 mL deionized waters are added dropwise, control drop rate avoids heat release acutely so that exploding, in this process The color of middle mixed solution becomes bronzing by blackish green.Flask is transferred in 80 DEG C of oil bath, keeps 15 min, then again It is transferred in 60 DEG C of oil bath, the hydrogen peroxide that 80 mL mass fractions are 3% is added dropwise under stirring condition, the color of solution is by red Brown becomes glassy yellow.Continue after stirring 10 min, by 2 h of flask stand.Supernatant is outwelled, by yellow mercury oxide with 5% dilute salt After acid elution 3 times, then it is washed with deionized 3 times.The solvent used in this chapter experiments is n-butanol, therefore is being washed three times Afterwards, continue to carry out alcohol with n-butanol to wash.Precipitation is transferred in Buchner funnel and is filtered, is washed three times with n-butanol again. Finally, the graphene solution of the high dispersive using n-butanol as dispersant has been obtained.After ultrasonic 1 h of graphene colloidal solution, claim Measure graphene solution bulk density：Weigh the quality m of empty surface plate1, the graphene solution of certain volume v is taken to be placed in table In the ware of face, weighing quality is m2, surface plate is transferred in air dry oven, it is m that its quality is weighed after being dried overnight3, pass through ρ =(m3-m1)/v measures graphene bulk density（20 mg mL-1）.
It takes 32 mL n-butanols to be added in beaker, 0.6 mL concentrated hydrochloric acids is added, then weigh 0.6 mmol SnCl2·2 H2O is added in beaker, stirs 10 min, continues 40 min of ultrasound, it is anti-that acquired mixed dispersion liquid is transferred to high temperature hydro-thermal It answers in kettle and obtains simple SnO in 180 DEG C of 2 h of hydro-thermal reaction2。
Weigh 3.2 mL（0.064 g）、6.4 mL（0.128 g）、9.6 mL（0.192 g）、17 mL（0.256 g）Oxygen Graphite alkene gel is added in beaker, takes the n-butanol of different volumes to be added in beaker so that the total volume of solution is 32 ML, is then added 0.6 mL concentrated hydrochloric acids, stirs 10 min, by 0.6 mmol SnCl under stirring condition2·2H2O is added to beaker In, 40 min are after graphene solution is completely dispersed ultrasound, and suspension obtained is transferred in hydrothermal reaction kettle in 180 DEG C of water The sediment alcohol of gained is washed and is washed 3 times after hydrothermal reaction kettle is cooled to room temperature and obtain graphene oxidation by 2 h of thermal response Tin composite 3DG@SnO2-1、3DG@SnO2-2、3DG@SnO2- 3 and 3DG@SnO2- 4, graphene oxidation tin composite is added Into the Tris solution of 10 mM, 10 min are stirred, 0.15 g Dopamine hydrochlorides are added, stirs 6 h under room temperature, solution is centrifuged It is washed 3 times with deionized water and ethyl alcohol afterwards, by product in -80 DEG C of 10 h of precooling, is then transferred in freeze drier and is lyophilized 48 h, then product is warming up to 550 DEG C of 3 h of calcining with the heating rate of 5 DEG C/min in a nitrogen atmosphere and makes cladding hydrochloric acid more The carbonization of bar amine, finally obtains the carbon-coated graphene tin oxide composite negative pole material 3DG SnO of N doping2@N-C-1、3DG@ SnO2@N-C-2、3DG@SnO2@N-C-3 and 3DG@SnO2@N-C-4。
Optimization analyzes graphene and SnO2Influence of the different proportion to electrode material high rate performance and cycle performance, most preferably Ratio product is in 100 mA g-1Current density under carry out charge and discharge, by can still be kept after 100 charge and discharge cycles 1349.5 mAh g-1Reversible capacity.Pass through higher current density and comes back to 200 mA g-1Carry out charge and discharge In the case of, still maintain 726 mAh g-1Relatively high reversible capacity.The 3DG@SnO that will be obtained2@N-C-2 and PVDF and conduction Carbon black is according to mass ratio 8:1:1 ratio is coated on copper foil, and thickness is about 60 μm, and it is diameter to be cut out copper foil with sheet-punching machine For the pole piece of 14 mm, 2025 button cells are assembled into, carry out electric performance test.
Fig. 1 is the SEM figures and TEM figures that pure zirconia graphene and tin oxide is made in the present embodiment, is passed through（a）With（b）It can be with See and has synthesized simple tin oxide nanoparticles during the experiment, while（c）With（d）In it can be seen that experimentation in The graphene oxide of simple three-dimensional structure is synthesized.
Fig. 2 is the SEM figures and TEM figures that material is made in the present embodiment, from Fig. 2（a）、（b）、（e）In it can be seen that three-dimensional stone The reticular structure of black alkene, from Fig. 2（c）In it can be seen that high uniformity dispersion SnO2Nano particle, size are about 18 nm. In Fig. 2（d）In black tab area have a thin layer of carbon, thickness is about 2.3 nm, and white dashed line tab area shows SnO2 Lattice fringe be 0.265 nm.Fig. 2（e）For 3DG@SnO2The low power number SEM figures of@N-C-2,（f）、（g）、（h）、（j）It is right It should be in Fig. 2（e）Middle 3DG@SnO2The Mapping of@N-C-2 schemes, it can be seen that C, O, Sn and N element are uniformly distributed, together When, the doping that N element is realized during carbon-coated has been proved again.
Fig. 3 is that sample 3DG@SnO are made in the present embodiment2The XRD analysis figure [email protected] as can be seen from Figure 3 The SnO of middle synthesis2And SnO2Standard card（Cassiterite, JCPDS No.41-1445）Diffraction maximum it is completely the same, this knot Fruit shows to have synthesized the SnO with high-purity2.In graphene oxide and SnO2After compound, the diffraction maximum of graphene disappears, This illustrates that graphene oxide is reduced into during high temperature as redox graphene.
Fig. 4 is the electro-chemical test figure that sample is made in the present embodiment.Fig. 4 is sample 3DG@SnO2@N-C-2 are in 100 mA g-1Current density under charge and discharge electrical image, it can be seen from the figure that the initial charge of the ratio sample and specific discharge capacity difference For 1977.7 mAh g-1With 1316.1 mAh g-1, coulombic efficiency reaches 66.5%, and passes through after 50 charge and discharge cycles, Still 1279.2 mAh g can be obtained-1Higher specific capacity.50th cycle and the 100th charge and discharge cycles as seen from the figure Charge and discharge electrical image almost overlaps, and shows that the sample of the ratio has preferable cycle performance, multiple in graphene and tin oxide During conjunction, the be capable of providing high specific capacity of conversion reaction is occurred into for the preferable three-dimensional structure of graphene and tin oxide just It is ideally combined togather, the structural intergrity of sample is maintained during cycle.
Fig. 6 is 3DG@SnO2High rate performance test charts of the@N-C-2 under different current densities.It can be clear from figure See, sample 3DG@SnO2@N-C-2 are in 200 mA g-1、400 mA g-1、600 mA g-1、800 mA g-1With 1 A g-1Electricity 857.1 mA g are maintained under current density respectively-1、722.7 mA g-1、651.3 mA g-1、578.1 mA g-1With 540.5 mAh g-1, and after high current density charge and discharge again with 200 mA g-1Current density charge and discharge when, reversible capacity according to 726 mAh g can so be reached-1。
Embodiment above describes the basic principles and main features and advantage of the present invention, and the technical staff of the industry should Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe the originals of the present invention Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within In the scope of protection of the invention.

Claims (2)

1. a kind of preparation method of three-dimensional grapheme tin oxide carbon compound cathode materials, it is characterised in that the specific steps are：It will The gel that 6.4 mL contain 0.128 g graphene oxides is added in beaker, is taken n-butanol to be added in beaker and is made solution Total volume is 32 mL, is then added 0.6 mL concentrated hydrochloric acids, stirs 10 min, by 0.6 mmol SnCl under stirring condition2·2 H2O is added in beaker, and 40 min are after graphene solution is completely dispersed ultrasound, and suspension obtained is transferred to hydro-thermal reaction In kettle and in 180 DEG C of 2 h of hydro-thermal reaction, after hydrothermal reaction kettle is cooled to room temperature, the sediment alcohol of gained is washed and washed 3 time Graphene oxidation tin composite is obtained, then graphene oxidation tin composite is added in the Tris solution of 10 mM, stirring 10 Min is added 0.15 g Dopamine hydrochlorides, stirs 6 h under room temperature, washed 3 times with deionized water and ethyl alcohol after solution is centrifuged, will Product is then transferred in freeze drier and 48 h is lyophilized in -80 DEG C of 10 h of precooling, then by product in nitrogen atmosphere with 5 DEG C/heating rate of min is warming up to 550 DEG C of 3 h of calcining and to coat Dopamine hydrochloride carbonization, finally obtain nitrogen-doped carbon cladding Graphene tin oxide composite negative pole material.
2. the preparation method of three-dimensional grapheme tin oxide carbon compound cathode materials according to claim 1, it is characterised in that： The three-dimensional grapheme tin oxide carbon compound cathode materials are the stannum oxide nano-crystal uniform loads by size uniformity in three-dimensional In graphene reticular structure, and carried out made from a step N doping and carbon coating using Dopamine hydrochloride as nitrogen source and carbon source, The size of middle stannum oxide nano-crystal is 8-18 nm.
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Publication number Priority date Publication date Assignee Title
CN109395762A (en) * 2018-11-29 2019-03-01 武汉工程大学 A kind of stannic oxide with core-shell structure/N doping graphite/zinc sulphide composite material and preparation method
CN110176589A (en) * 2019-05-31 2019-08-27 上海大学 The tin oxide base negative electrode material and preparation method of poly-dopamine cladding
CN111068647A (en) * 2020-01-02 2020-04-28 南京工程学院 Nano TiO (titanium dioxide)2-SnO2Preparation method of solid solution photocatalytic material

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CN103887488A (en) * 2014-04-04 2014-06-25 哈尔滨工业大学 Preparation method of peach-kernel-shaped SnO2-graphene-carbon composite material for lithium ion battery
CN104900859A (en) * 2015-06-01 2015-09-09 合肥工业大学 Porous SnO2 nano ball/graphene composite material and preparation method thereof
CN105226260A (en) * 2015-10-19 2016-01-06 中南大学 A kind of preparation method of lithium ion battery silicon based anode material
CN105742635A (en) * 2016-01-01 2016-07-06 三峡大学 Stannic oxide/graphene/carbon composite material and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN103887488A (en) * 2014-04-04 2014-06-25 哈尔滨工业大学 Preparation method of peach-kernel-shaped SnO2-graphene-carbon composite material for lithium ion battery
CN104900859A (en) * 2015-06-01 2015-09-09 合肥工业大学 Porous SnO2 nano ball/graphene composite material and preparation method thereof
CN105226260A (en) * 2015-10-19 2016-01-06 中南大学 A kind of preparation method of lithium ion battery silicon based anode material
CN105742635A (en) * 2016-01-01 2016-07-06 三峡大学 Stannic oxide/graphene/carbon composite material and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109395762A (en) * 2018-11-29 2019-03-01 武汉工程大学 A kind of stannic oxide with core-shell structure/N doping graphite/zinc sulphide composite material and preparation method
CN110176589A (en) * 2019-05-31 2019-08-27 上海大学 The tin oxide base negative electrode material and preparation method of poly-dopamine cladding
CN111068647A (en) * 2020-01-02 2020-04-28 南京工程学院 Nano TiO (titanium dioxide)2-SnO2Preparation method of solid solution photocatalytic material
CN111068647B (en) * 2020-01-02 2022-12-09 南京工程学院 Nano TiO (titanium dioxide) 2 -SnO 2 Method for preparing solid solution photocatalytic material

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