CN109301204A - A kind of preparation method of hollow ball structure artificial gold/tin oxide lithium ion battery negative material - Google Patents

A kind of preparation method of hollow ball structure artificial gold/tin oxide lithium ion battery negative material Download PDF

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CN109301204A
CN109301204A CN201811115850.0A CN201811115850A CN109301204A CN 109301204 A CN109301204 A CN 109301204A CN 201811115850 A CN201811115850 A CN 201811115850A CN 109301204 A CN109301204 A CN 109301204A
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lithium ion
ion battery
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sno
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CN109301204B (en
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殷立雄
蔺英
程如亮
张浩繁
黄剑锋
白培杰
李慧敏
宋佳琪
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Shaanxi University of Science and Technology
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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
    • 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
    • H01M4/58—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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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 hollow ball structure artificial gold/tin oxide lithium ion battery negative material, by SnCl4·5H2O is dissolved in the mixed liquor of deionized water and dehydrated alcohol, is dissolved it sufficiently and is formed solution A, NaOH is dissolved in solution A and is configured to solution B；Urea is added in B solution under stirring, persistently stirs into homogeneous mixture solotion C, mixed solution C is then subjected to homogeneous hydro-thermal reaction；To after reaction, washed drying to obtain SnO2Presoma；By SnO2Presoma heating calcination obtains SnO2Powder；By SnO2Powder disperses in ethanol and stirs, and obtains uniformly mixed suspension D；SnCl is added into suspension D4·5H2O and TAA, stirring is until be completely dissolved to form uniform suspension E；Suspension E is subjected to microwave hydrothermal reaction, to after reaction, take out product, washed drying to obtain hollow ball structure artificial gold/tin oxide lithium ion battery negative material.

Description

A kind of preparation of hollow ball structure artificial gold/tin oxide lithium ion battery negative material Method
Technical field
The present invention relates to a kind of preparation methods of lithium ion battery negative material, and in particular to a kind of hollow ball structure vulcanization Tin/tin oxide lithium ion battery negative material preparation method.
Background technique
As the mankind enter informationized society, the various high-tech such as mobile phone, digital camera, laptop are portable Electronic product is gradually popularized, consequent be the demand of people's movable small power supply high to safety, performance sharply Increase.Lithium ion battery is a kind of mechanism of new electrochemical power sources, and small in size, light weight, the energy for meeting that required by electronic product wants are close The application requirements such as degree is high, has extended cycle life, has a safety feature and can be quickly charged and discharged, therefore become the heat of research and application at present Point.The problem of there are many but still, needs to solve, such as: at high cost, capacity requirement and cycle performance are inadequate, this wants us Suitable battery material is researched and developed as emphasis.
SnS2It is the binary compound for belonging to IV:VI main group, by hexagonal phase basic unit CdI2Layered crystal structure (structure cell Parameter: a=0.3648nm, c=0.5899nm) composition, this structural unit among the sulphion of two layers of hexagonal closs packing by adding Enter sandwich structure (S-Sn-S) composition of tin ion.Every six sulphions are inserted into a tin ion formation regular octahedron and match Position, and there is weak Van der Waals force between layers and pass through Covalent bonding together.In addition, there are many crystalline substances for this layer structure Body vacancy can be used as the host lattice of intercalation.People are partly led using the special performance that these different structures possess to prepare Body material, catalysis material, solar cell material, photo-translating system material and lithium ion battery material etc..It is unique It performance and is widely applied so that SnS2Material becomes one of the material for most having application prospect.Moreover, SnS2Due to its high theoretical appearance Measure (690mAhg-1), natural resources abundant, nontoxicity and low cost, it is considered to be negative electrode material of new generation it is promising Candidate, but it is also the same with most of negative electrode materials, it is big there are volume expansion in poorly conductive, charge and discharge process the disadvantages of, Limit its development as lithium ion battery negative material.
Nano SnO2With quantum size effect, thus it can have broader forbidden bandwidth, Senthilkumar et al. Prove nano SnO2Particle size is smaller, and forbidden bandwidth is bigger, and highest may be up to 4.26eV.Because intrinsic with nano material Small-size effect and skin effect all show special effect in terms of light absorption, photocatalysis and air-sensitive, are depositing Storage material, gas sensor, catalysis material, electrode material and solar cell material etc. have all widely been studied And application.Equally, SnO2Due to its high theoretical capacity (782mAh/g), natural resources abundant, nontoxicity and low cost, also by It is considered the promising candidate of negative electrode material of new generation and is widely studied.Thus, by SnS2With SnO2Carry out it is compound, into And improve its chemical property as lithium ion battery negative material.
Currently, SnS2/SnO2Preparation method mainly have two-step method (solvent-thermal method and heat treating process) [Wang W, Xu C, Wang X,et al.Preparation of SnO2 nanorods by annealing SnO2 powder in NaCl Flux [J] .Journal of Materials Chemistry, 2002,12 (6): 1922-1925.], electrostatic spinning technique and Heat treating process [Li Y Y, Wang J G, Sun H H, et al.Heterostructured SnS2/SnO2, nanotubes with enhanced charge separation and excellent photocatalytic hydrogen Production [J] .International Journal of Hydrogen Energy, 2018.] etc..Solvent thermal reaction method It is a kind of improved hydro-thermal reaction method, replaces traditional water to make solvent with organic solvent, but reaction process needs strict control molten The condition of agent heat.Thermal decomposition method operation is simple, and reaction rate is fast, but product is easily caused to reunite, and reaction required temperature is higher, It is higher to energy and cost requirement needed for producing.Electrostatic spinning yield is unstable, and inefficiency, can only there is 0.1g/h per hour ~1g/h causes huge obstruction to the extensive use of its industrialization, scale and nano-fiber material, is not able to satisfy tradition Demand of the market to the dosage of nanofiber.
Summary of the invention
The purpose of the present invention is to provide a kind of hollow ball structure SnS2/SnO2The preparation side of lithium ion battery negative material Method, to overcome the problems of the above-mentioned prior art, preparation cost of the present invention is low, easy to operate, short preparation period, the sky of acquisition The SnS of bulbus cordis structure2/SnO2It is preferable as lithium ion battery negative material capacity height, cyclical stability.
In order to achieve the above objectives, the present invention adopts the following technical scheme:
A kind of preparation method of hollow ball structure artificial gold/tin oxide lithium ion battery negative material, comprising the following steps:
1) by SnCl4·5H2O is dissolved in the mixed liquor of deionized water and dehydrated alcohol, is dissolved it sufficiently and is formed solution A, According to element mass ratio mSn:mNa=(0.5~1): NaOH is dissolved in solution A by (0.6~0.95) is configured to solution B；
2) urea is added in B solution under stirring, persistently stirs into homogeneous mixture solotion C, and SnCl4· 5H2The mass ratio of O and urea is (0.5~1): then mixed solution C is carried out homogeneous hydro-thermal reaction by (0.3~0.7)；
3) to after reaction, product be distinguished centrifuge washing several times through deionized water and dehydrated alcohol, then vacuum Drying to obtain SnO2Presoma；
4) by SnO2Presoma heats 1~5h under the conditions of 300 DEG C~500 DEG C, and heating rate is controlled in 1-5 DEG C/min, When temperature drops to room temperature to get arrive SnO2Powder；
5) by SnO2Powder disperses in ethanol and stirs, and obtains uniformly mixed suspension D；
6) by SnCl4·5H2O and TAA presses elemental mole ratios nSn: nS=1:(1~4) be added suspension D in, stirring until It is completely dissolved to form uniform suspension E；
7) suspension E is subjected to microwave hydrothermal reaction, to after reaction, product be taken out, through deionized water and anhydrous second Alcohol distinguishes centrifuge washing several times, and then vacuum drying obtains hollow ball structure artificial gold/tin oxide negative electrode of lithium ion battery Material.
Further, dissolved in the mixed liquor of every 60mL deionized water and dehydrated alcohol in step 1) 0.5g~ 1gSnCl4·5H2O。
Further, V in the mixed liquor of deionized water and dehydrated alcohol in step 1)Deionized water: VDehydrated alcohol=1:5~5:1.
Further, mixed solution C is subjected to homogeneous hydro-thermal reaction in step 2) specifically: be put into mixed solution C The sealing of phase hydrothermal reaction kettle, packing ratio control are put into homogeneous hydro-thermal reaction instrument 40%~60%, and reaction temperature is controlled 160 ~200 DEG C, the reaction time controls in 12~30h.
Further, vacuum drying temperature is 80 DEG C in step 3) and step 7), time 12h.
Further, disperse 0.25g~0.45g SnO in step 5) in every 40~60mL ethyl alcohol2Powder.
Further, 0.5-1.5gSnCl is added in every 40~60mL suspension D in step 6)4·5H2O。
Further, suspension E is subjected to microwave hydrothermal reaction in step 7) specifically: suspension E is put into Microwave Water In hot kettle, 1~5h is reacted at 160~200 DEG C.
Compared with prior art, the invention has the following beneficial technical effects:
Hollow ball structure SnS prepared by the present invention2/SnO2, it is improved in charge and discharge as lithium ion battery negative material Structural stability, alleviation volume expansion and improvement chemical property, hollow ball structure prepared by the present invention in cyclic process is same Other structures are compared, and are had many advantages, such as that light weight, specific surface area are bigger, can be increased reactivity site, are conducive to increase Li+Diffusion admittance, Li+Migration distance can also shorten, be more advantageous to the promotion of lithium ion battery negative material performance in this way, separately Outer reaction rate of the present invention is very fast, and reaction is sufficiently thorough, and product crystallinity is strong, pattern is special, grain growth is controllable and size point Cloth is uniform, it eliminates the thermal loss of traditional heating mode, have heating speed is fast, homogeneous heating without temperature gradient, without stagnant The features such as aftereffect, the experimental results showed that in 300mAg-1Discharge capacity can reach 1679.6mAhg for the first time under current density-1, capacity is maintained at 575.6mAhg after circulation 50 is enclosed-1, there is good cyclical stability.
Detailed description of the invention
Fig. 1 is SnS prepared by example 2 of the present invention2/SnO2The XRD diagram of lithium ion battery negative material；
Fig. 2 is the SnS of hollow ball structure prepared by example 2 of the present invention2/SnO2The SEM of cell negative electrode material schemes；
Fig. 3 is SnS prepared by example 2 of the present invention2/SnO2Cell negative electrode material in 300mAg-1It is followed under current density Ring performance map.
Specific embodiment
Embodiments of the present invention are described in further detail below:
1) by 0.5g~1gSnCl4·5H2O is dissolved in (V in 60mL deionized water and dehydrated alcoholDeionized water: VDehydrated alcohol=1:5~ 5:1), it dissolves it sufficiently and forms solution A, according to element mass ratio mSn:mNa=(0.5~1:(0.6~0.95) is molten by NaOH Solution B is configured in above-mentioned solution A；
2) 0.3g~0.7g urea is added in B solution under magnetic agitation effect, persistently stir into uniformly mix it is molten Liquid C, and C solution is put into homogeneous hydrothermal reaction kettle and is sealed, packing ratio is controlled 40%~60%, is put into homogeneous hydro-thermal reaction Instrument, at 160~200 DEG C, the reaction time is controlled in 12~30h for reaction temperature control；
3) to after reaction, take out presoma, distinguish centrifuge washing 3 times through deionized water and dehydrated alcohol, obtain white Color presoma is dried in vacuo 12h under the conditions of 80 DEG C and obtains SnO2Presoma；
4) carry out 1~5h of heating in Muffle furnace under the conditions of 300 DEG C~500 DEG C, heating rate control 1-5 DEG C/ Min opens Muffle furnace when temperature drops to room temperature and takes out porcelain boat, resulting tiny powdered samples, as SnO2Powder；
5) by above-mentioned prepared SnO2Material weighs 0.25~0.45g and is dispersed in 40~60ml ethyl alcohol simultaneously magnetic agitation 1h obtains uniformly mixed suspension D；
6) it is given in above-mentioned suspension by elemental mole ratios and n is addedSn: nS=1:(1~4) to being added in above-mentioned suspension D SnCl4·5H2O and TAA (thioacetamide) stirring is until be completely dissolved to form uniform suspension E, every 40~60mL suspension 0.5-1.5gSnCl is added in D4·5H2O；
7) the suspension E of acquired different proportion tin sulphur ratio is put into microwave hydrothermal kettle, under microwave condition for 160~ 1~5h is reacted at 200 DEG C obtains presoma later.To after reaction, take out presoma, through deionized water and dehydrated alcohol point It is dried in vacuo 12h at other centrifuge washing 3 times, 80 DEG C and obtains SnS2/SnO2Presoma.
Below with reference to embodiment, the invention will be described in further detail:
Embodiment 1
1) by 0.5g SnCl4·5H2O is dissolved in (V in 60mL deionized water and dehydrated alcoholDeionized water: VDehydrated alcohol=1:5), make It, which is sufficiently dissolved, forms solution A, according to element mass ratio mSn:mNaNaOH is dissolved in above-mentioned solution A by=(0.5:0.6) to be prepared At solution B；
2) 0.3g urea is added in B solution under magnetic agitation effect, persistently stirs into homogeneous mixture solotion C, and C solution is put into homogeneous hydrothermal reaction kettle sealing, packing ratio is controlled 40%, is put into homogeneous hydro-thermal reaction instrument, reaction temperature control At 160 DEG C, the reaction time controls in 12h system；
3) to after reaction, take out presoma, distinguish centrifuge washing 3 times through deionized water and dehydrated alcohol, obtain white Color presoma is dried in vacuo 12h under the conditions of 80 DEG C and obtains SnO2Presoma；
4) heating 1h is carried out in Muffle furnace under the conditions of 300 DEG C, heating rate is controlled in 1 DEG C/min, dropped to temperature Muffle furnace is opened when room temperature takes out porcelain boat, resulting tiny powdered samples, as SnO2Powder；
5) by above-mentioned prepared SnO2Material weighs 0.25g and is dispersed in 40ml ethyl alcohol simultaneously magnetic agitation 1h, is mixed Close uniform suspension D；
6) it is given in above-mentioned suspension liquid by elemental mole ratios and n is addedSn: nS=1:1 gives in above-mentioned suspension D and is added SnCl4·5H2O and TAA (thioacetamide) stirring is until be completely dissolved to form uniform suspension E, in every 40mL suspension D 0.5gSnCl is added4·5H2O；
7) suspension E is put into microwave hydrothermal kettle, is under microwave condition to obtain forerunner after reacting 1h at 160 DEG C Body.To after reaction, take out presoma, it is dried in vacuo at distinguishing centrifuge washing 3 times, 80 DEG C through deionized water and dehydrated alcohol 12h obtains SnS2/SnO2Presoma.
Embodiment 2
1) by 0.7102g SnCl4·5H2O is dissolved in (V in 60mL deionized water and dehydrated alcoholDeionized water: VDehydrated alcohol=1:1), It dissolves it sufficiently and forms solution A, according to element mass ratio mSn:mNaNaOH is dissolved in above-mentioned solution by=(0.7102:0.8002) Solution B is configured in A；
2) 0.5g urea is added in B solution under magnetic agitation effect, persistently stirs into homogeneous mixture solotion C, and C solution is put into homogeneous hydrothermal reaction kettle sealing, packing ratio is controlled 50%, is put into homogeneous hydro-thermal reaction instrument, reaction temperature control At 180 DEG C, the reaction time controls for 24 hours system；
3) to after reaction, take out presoma, distinguish centrifuge washing 3 times through deionized water and dehydrated alcohol, obtain white Color presoma is dried in vacuo 12h under the conditions of 80 DEG C and obtains SnO2Presoma；
4) heating 3h is carried out in Muffle furnace under the conditions of 400 DEG C, heating rate is controlled in 2 DEG C/min, dropped to temperature Muffle furnace is opened when room temperature takes out porcelain boat, resulting tiny powdered samples, as SnO2Powder；
5) by above-mentioned prepared SnO2Material weighs 0.3104g and is dispersed in 50ml ethyl alcohol simultaneously magnetic agitation 1h, obtains Uniformly mixed suspension D；
6) it is given in above-mentioned suspension liquid by elemental mole ratios and n is addedSn: nS=1:2 gives in above-mentioned suspension D and is added SnCl4·5H2O and TAA (thioacetamide) stirring is until be completely dissolved to form uniform suspension E；In every 60mL suspension D 1.5gSnCl is added4·5H2O
7) suspension E is put into microwave hydrothermal kettle, is under microwave condition to obtain forerunner after reacting 3h at 180 DEG C Body.To after reaction, take out presoma, it is dried in vacuo at distinguishing centrifuge washing 3 times, 80 DEG C through deionized water and dehydrated alcohol 12h obtains SnS2/SnO2Presoma.
As can be seen from Figure 1 SnS prepared by the present embodiment2/SnO2Crystallinity is preferable, and product purity is preferable, from Fig. 2 It can be seen that the SnS of hollow ball structure prepared by the present embodiment2/SnO2The diameter of cell negative electrode material is about 500nm- 900nm；From figure 3, it can be seen that using product manufactured in the present embodiment as lithium ion battery negative material discharge capacity for the first time It can reach 1679.6mAhg-1, capacity is maintained at 575.6mAhg after circulation 50 is enclosed-1, there is good cyclical stability.
Embodiment 3
1) by 1g SnCl4·5H2O is dissolved in (V in 60mL deionized water and dehydrated alcoholDeionized water: VDehydrated alcohol=5:1), make it Sufficiently dissolution forms solution A, according to element mass ratio mSn:mNa=(1:0.95) NaOH is dissolved in above-mentioned solution A be configured to it is molten Liquid B；
2) 0.7g urea is added in B solution under magnetic agitation effect, persistently stirs into homogeneous mixture solotion C) it will C solution is put into homogeneous hydrothermal reaction kettle sealing, and packing ratio control is put into homogeneous hydro-thermal reaction instrument, reaction temperature control 60% At 200 DEG C, the reaction time is controlled in 30h；
3) to after reaction, take out presoma, distinguish centrifuge washing 3 times through deionized water and dehydrated alcohol, obtain white Color presoma is dried in vacuo 12h under the conditions of 80 DEG C and obtains SnO2Presoma.
4) heating 5h is carried out in Muffle furnace under the conditions of 500 DEG C, heating rate control waits for that temperature drops to room in 5 DEG C/min Muffle furnace is opened when warm takes out porcelain boat, resulting tiny powdered samples, as SnO2。
5) by above-mentioned prepared SnO2Material weighs 0.45g and is dispersed in 60ml ethyl alcohol simultaneously magnetic agitation 1h, is mixed Close uniform suspension D；
6) it is given in above-mentioned suspension liquid by elemental mole ratios and n is addedSn: nS=1:4 gives in above-mentioned suspension D and is added SnCl4·5H2O and TAA (thioacetamide) stirring is until be completely dissolved to form uniform suspension E；In every 50mL suspension D 1gSnCl is added4·5H2O
7) suspension E is put into microwave hydrothermal kettle, is under microwave condition to obtain forerunner after reacting 5h at 200 DEG C Body.To after reaction, take out presoma, it is dried in vacuo at distinguishing centrifuge washing 3 times, 80 DEG C through deionized water and dehydrated alcohol 12h obtains SnS2/SnO2Presoma.

Claims (8)

1. a kind of preparation method of hollow ball structure artificial gold/tin oxide lithium ion battery negative material, which is characterized in that including Following steps:
1) by SnCl4·5H2O is dissolved in the mixed liquor of deionized water and dehydrated alcohol, is dissolved it sufficiently and is formed solution A, according to Element mass ratio mSn:mNa=(0.5~1): NaOH is dissolved in solution A by (0.6~0.95) is configured to solution B；
2) urea is added in B solution under stirring, persistently stirs into homogeneous mixture solotion C, and SnCl4·5H2O and The mass ratio of urea is (0.5~1): then mixed solution C is carried out homogeneous hydro-thermal reaction by (0.3~0.7)；
3) to after reaction, product be distinguished centrifuge washing several times through deionized water and dehydrated alcohol, is then dried in vacuo Obtain SnO2Presoma；
4) by SnO2Presoma heats 1~5h under the conditions of 300 DEG C~500 DEG C, and heating rate is controlled in 1-5 DEG C/min, to temperature To get to SnO when dropping to room temperature2Powder；
5) by SnO2Powder disperses in ethanol and stirs, and obtains uniformly mixed suspension D；
6) by SnCl4·5H2O and TAA presses elemental mole ratios nSn: nS=1:(1~4) it is added in suspension D, stirring is until completely Dissolution forms uniform suspension E；
7) suspension E is subjected to microwave hydrothermal reaction, to after reaction, take out product, through deionized water and dehydrated alcohol point Several times, then vacuum drying obtains hollow ball structure artificial gold/tin oxide lithium ion battery negative material to other centrifuge washing.
2. a kind of preparation of hollow ball structure artificial gold/tin oxide lithium ion battery negative material according to claim 1 Method, which is characterized in that dissolve in 0.5g~1gSnCl in the mixed liquor of every 60mL deionized water and dehydrated alcohol in step 1)4· 5H2O。
3. a kind of preparation of hollow ball structure artificial gold/tin oxide lithium ion battery negative material according to claim 1 Method, which is characterized in that V in the mixed liquor of deionized water and dehydrated alcohol in step 1)Deionized water: VDehydrated alcohol=1:5~5:1.
4. a kind of preparation of hollow ball structure artificial gold/tin oxide lithium ion battery negative material according to claim 1 Method, which is characterized in that mixed solution C is subjected to homogeneous hydro-thermal reaction in step 2) specifically: be put into mixed solution C homogeneously Hydrothermal reaction kettle sealing, packing ratio control are put into homogeneous hydro-thermal reaction instrument 40%~60%, reaction temperature control 160~ 200 DEG C, the reaction time controls in 12~30h.
5. a kind of preparation of hollow ball structure artificial gold/tin oxide lithium ion battery negative material according to claim 1 Method, which is characterized in that vacuum drying temperature is 80 DEG C in step 3) and step 7), time 12h.
6. a kind of preparation of hollow ball structure artificial gold/tin oxide lithium ion battery negative material according to claim 1 Method, which is characterized in that disperse 0.25g~0.45g SnO in step 5) in every 40~60mL ethyl alcohol2Powder.
7. a kind of preparation of hollow ball structure artificial gold/tin oxide lithium ion battery negative material according to claim 1 Method, which is characterized in that 0.5-1.5gSnCl is added in every 40~60mL suspension D in step 6)4·5H2O。
8. a kind of preparation of hollow ball structure artificial gold/tin oxide lithium ion battery negative material according to claim 1 Method, which is characterized in that suspension E is subjected to microwave hydrothermal reaction in step 7) specifically: suspension E is put into microwave hydrothermal In kettle, 1~5h is reacted at 160~200 DEG C.
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CN110255605A (en) * 2019-06-21 2019-09-20 新疆大学 A kind of solid phase prepares tin oxide-artificial gold hetero-junctions nano flower method
CN111180707A (en) * 2020-01-14 2020-05-19 中南大学 Tin diselenide/tin oxide-rGO nano composite anode material and preparation method thereof
CN111589456A (en) * 2020-03-09 2020-08-28 浙江理工大学 Carbon fiber cloth @ SnO2@SnS2Heterojunction and method for manufacturing the same
CN112366319A (en) * 2019-12-31 2021-02-12 广东天劲新能源科技股份有限公司 Composite nano SnO2Preparation method of negative electrode material and mesocarbon microbeads
CN113991084A (en) * 2021-10-27 2022-01-28 西安建筑科技大学 SnS-SnO2-GO @ C heterostructure composite material and preparation method and application thereof
CN116282136A (en) * 2023-05-25 2023-06-23 新乡学院 Preparation method of in-situ vertically grown tin sulfide nanosheets

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101609886A (en) * 2009-07-16 2009-12-23 浙江大学 A kind of preparation lithium ion battery SnO 2/ SnS 2The method of nanometer combined electrode material
CN102086044A (en) * 2009-12-03 2011-06-08 中国科学院宁波材料技术与工程研究所 Method for preparing hollow spherical stannic oxide nano powder
CN105098181A (en) * 2015-08-13 2015-11-25 陕西科技大学 Preparation method for nano-flake SnS2 sodium-ion battery negative electrode material with good rate capability
CN106129344A (en) * 2016-06-06 2016-11-16 重庆大学 A kind of tin ash/Titanium dioxide spherical granule and the preparation method of graphene nano belt composite

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101609886A (en) * 2009-07-16 2009-12-23 浙江大学 A kind of preparation lithium ion battery SnO 2/ SnS 2The method of nanometer combined electrode material
CN102086044A (en) * 2009-12-03 2011-06-08 中国科学院宁波材料技术与工程研究所 Method for preparing hollow spherical stannic oxide nano powder
CN105098181A (en) * 2015-08-13 2015-11-25 陕西科技大学 Preparation method for nano-flake SnS2 sodium-ion battery negative electrode material with good rate capability
CN106129344A (en) * 2016-06-06 2016-11-16 重庆大学 A kind of tin ash/Titanium dioxide spherical granule and the preparation method of graphene nano belt composite

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
KE WANG等: ""Synthesis of Hollow SnO2/SnS2 Hybrids and Their Application in Sodium-Ion Batteries"", 《CHEMELECTROCHEM》 *
RUIQING LIU等: ""Template-free synthesis of SnO2 hollow microspheres as anode material for lithium-ion battery"", 《MATERIALS LETTERS》 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110255605A (en) * 2019-06-21 2019-09-20 新疆大学 A kind of solid phase prepares tin oxide-artificial gold hetero-junctions nano flower method
CN112366319A (en) * 2019-12-31 2021-02-12 广东天劲新能源科技股份有限公司 Composite nano SnO2Preparation method of negative electrode material and mesocarbon microbeads
CN112366319B (en) * 2019-12-31 2022-06-14 广东天劲新能源科技股份有限公司 Composite nano SnO2Preparation method of negative electrode material and mesocarbon microbeads
CN111180707A (en) * 2020-01-14 2020-05-19 中南大学 Tin diselenide/tin oxide-rGO nano composite anode material and preparation method thereof
CN111180707B (en) * 2020-01-14 2022-03-11 中南大学 Tin diselenide/tin oxide-rGO nano composite anode material and preparation method thereof
CN111589456A (en) * 2020-03-09 2020-08-28 浙江理工大学 Carbon fiber cloth @ SnO2@SnS2Heterojunction and method for manufacturing the same
CN111589456B (en) * 2020-03-09 2023-04-14 浙江理工大学 Carbon fiber cloth @ SnO 2 @SnS 2 Heterojunction and method for manufacturing the same
CN113991084A (en) * 2021-10-27 2022-01-28 西安建筑科技大学 SnS-SnO2-GO @ C heterostructure composite material and preparation method and application thereof
CN116282136A (en) * 2023-05-25 2023-06-23 新乡学院 Preparation method of in-situ vertically grown tin sulfide nanosheets
CN116282136B (en) * 2023-05-25 2024-03-22 新乡学院 Preparation method of in-situ vertically grown tin sulfide nanosheets

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