CN105552351B - A kind of spherical SnO of nano particle assembling2Anode material of lithium-ion battery and preparation method thereof - Google Patents

A kind of spherical SnO of nano particle assembling2Anode material of lithium-ion battery and preparation method thereof Download PDF

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CN105552351B
CN105552351B CN201610049651.9A CN201610049651A CN105552351B CN 105552351 B CN105552351 B CN 105552351B CN 201610049651 A CN201610049651 A CN 201610049651A CN 105552351 B CN105552351 B CN 105552351B
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solution
lithium
ion battery
anode material
nano particle
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CN105552351A (en
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殷立雄
柴思敏
刘长青
马建中
黄剑锋
王菲菲
孔新刚
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Shaanxi University of Science and Technology
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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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention discloses a kind of spherical SnO of nano particle assembling2Anode material of lithium-ion battery and preparation method thereof, including：1) by SnCl4·5H2O is dissolved in deionized water, is configured to solution A；PVP is added in solution A, sodium citrate is added in aliquots of deionized water, solution B is configured to；2) B solution is slowly added to solution A under continuing magnetic force stirring action and forms homogeneous solution C, N is added dropwise into solution CaOH solution Es form solution D；3) homogeneous hydro-thermal reaction is carried out；4) it waits for after reaction, taking out presoma, washing obtains white presoma, and freeze-drying presoma obtains nano particle and assembles spherical SnO2Anode material of lithium-ion battery.Preparation method of the present invention has the characteristics that manufacturing cost is low, easy to operate, short preparation period, and prepared particle assembles spherical SnO2Anode material of lithium-ion battery is under the current density of 100mA/g, and discharge capacity can reach 409mAh/g for the first time, and after recycling 70 times, capacity is positively retained at 225.8mAh g‑1, there is preferable cyclical stability.

Description

A kind of spherical SnO of nano particle assembling2Anode material of lithium-ion battery and its preparation Method
Technical field
The present invention relates to sodium-ion battery technical field, more particularly to a kind of anode material of lithium-ion battery and its preparation side Method.
Background technology
Sodium-ion battery is a kind of model electrochemical power supply, has that raw material resources are abundant, cost is relatively low, specific capacity and effect The advantages that rate is higher more meets the requirement of scale stored energy application, is promoting extensive regenerative resource grid integration ability, is carrying There is application potential, simultaneously because its specific capacity height, light weight, long lifespan and nothing in terms of high electric energy service efficiency and power quality The significant advantages such as Memorability also have extensive in fields such as aerospace, hybrid-electric car and portable electronic devices Using.In this context, sodium-ion battery causes the extensive concern in worldwide, critical material and related skill in recent years Art progress is rapid.But for opposite lithium ion, sodium ion has larger ionic radius (0.102nm vs.0.076nm Of Li), this so that finding suitable embedding sodium material tool acquires a certain degree of difficulty.
Invention content
The purpose of the present invention is to provide a kind of nano particles to assemble spherical SnO2Anode material of lithium-ion battery and its system Preparation Method, manufacturing cost is low, easy to operate, short preparation period, and the particle of acquisition assembles spherical SnO2Sodium-ion battery cathode Excellent material performance.
To achieve the goals above, the present invention adopts the following technical scheme that：
A kind of spherical SnO of nano particle assembling2The preparation method of anode material of lithium-ion battery, includes the following steps：
1) by SnCl4·5H2O is dissolved in deionized water, is configured to solution A；SnCl in mass ratio4·5H2O：PVP：Lemon Sour sodium=1:(0.4~1.5):(0.4~1.5) PVP is added in solution A, and sodium citrate is added in aliquots of deionized water, is matched Solution B is made；
2) B solution is slowly added to solution A under continuing magnetic force stirring action and forms homogeneous solution C, dropwise into solution C N is addedaOH solution Es form solution D；The volume of solution C and the volume ratio of solution E are 5:1~2:4；
3) it waits for after reaction, solution D being put into hydrothermal reaction kettle and is sealed, carries out homogeneous hydro-thermal reaction；
4) it waits for after reaction, taking out presoma, washing obtains white presoma, and freeze-drying presoma obtains nanometer Grain assembles spherical SnO2Anode material of lithium-ion battery.
Further, in solution A Sn a concentration of 0.5~1.2mol/L.
Further, NaThe solubility of OH solution Es is 0.3~1.2mol/L.
Further, the condition of homogeneous hydro-thermal reaction is：At 100~220 DEG C, reaction time control exists for reaction temperature control 8~48h.
Further, the washing is specially to distinguish centrifuge washing 2~3 times through deionized water and absolute ethyl alcohol.
Further, the freeze-drying is specially that prepared presoma is subzero in the freezing chamber of freeze drier 50-60 DEG C of freezing 4-5h, then dries 10-12h at room temperature in vacuum drying cabinet.
A kind of spherical SnO of nano particle assembling2Nano particle prepared by the preparation method of anode material of lithium-ion battery Assemble spherical SnO2Anode material of lithium-ion battery.
Compared with the existing technology, the invention has the advantages that：
A kind of nano particle of the present invention assembles spherical SnO2The preparation method of anode material of lithium-ion battery has and is prepared into The characteristics of this is low, easy to operate, short preparation period, prepared particle assemble spherical SnO2Anode material of lithium-ion battery particle Size only has a few to tens of nanometers, and assembling ball size is about 300~400nm, and purity is high, crystallinity is strong, pattern is uniform, is answered For sodium-ion battery cathode, under the current density of 100mA/g, discharge capacity can reach 409mAh/g, cycle 70 for the first time After secondary, capacity is positively retained at 225.8mAh g-1, there is preferable cyclical stability.
Description of the drawings
Fig. 1 is that the nano particle prepared by the embodiment of the present invention 1 assembles spherical SnO2The SEM of anode material of lithium-ion battery Figure.
Fig. 2 is that the nano particle prepared by the embodiment of the present invention 1 assembles spherical SnO2Anode material of lithium-ion battery electrification Learn performance map.
Specific implementation mode
Embodiment 1
A kind of spherical SnO of nano particle assembling2The preparation method of anode material of lithium-ion battery, includes the following steps：
1) by SnCl4·5H2O is dissolved in deionized water, is configured to the solution A of a concentration of 0.5mol/L；In mass ratio mSnCl4·5H2O： mPVP：mNa3C6H5O7=1:0.4:0.4 plasdone (PVP) is added in solution A, by citric acid Sodium (Na3C6H5O7) be added in aliquots of deionized water, it is configured to solution B；
2) B solution is slowly added to solution A under continuing magnetic force stirring action and forms homogeneous solution C, dropwise into solution C 0.3mol/L N are addedaOH solution Es form solution D, persistently stir 0.5h afterwards；The volume of solution C and the volume ratio of solution E are 5:1；
3) it waits for after reaction, solution D being put into hydrothermal reaction kettle and is sealed, is put into homogeneous hydro-thermal reaction instrument, reaction temperature At 100 DEG C, the reaction time controls in 8h for degree control；
4) it waits for after reaction, taking out presoma, distinguishes centrifuge washing 2 times through deionized water and absolute ethyl alcohol, obtain white Color presoma, by institute's presoma freeze drier freezing chamber it is subzero 50 DEG C freezing 5h, then vacuum drying cabinet at room temperature Dry 10h obtains nano particle and assembles spherical SnO2Anode material of lithium-ion battery.
Fig. 1 is that the nano particle prepared by the embodiment of the present invention 1 assembles spherical SnO2The SEM of anode material of lithium-ion battery Figure.As can be seen from the figure the surface of sample is to be assembled by nano particle spherical, and nanoparticle size is about more than ten nanometers, The grain size for assembling ball is about 300~400nm.Fig. 2 is that the nano particle prepared by the embodiment of the present invention 1 assembles spherical SnO2Sodium from Sub- cell negative electrode material chemical property figure.As can be seen from the figure prepared particle assembles spherical SnO2Sodium-ion battery cathode Material is under the current density of 100mA/g, and discharge capacity can reach 409mAh/g for the first time, and after recycling 70 times, capacity can be protected It holds in 225.8mAh g-1, there is preferable cyclical stability.
Embodiment 2
A kind of spherical SnO of nano particle assembling2The preparation method of anode material of lithium-ion battery, includes the following steps：
1) by SnCl4·5H2O is dissolved in deionized water, is configured to the solution A of a concentration of 0.5mol/L；In mass ratio mSnCl4·5H2O： mPVP：mNa3C6H5O7=1:0.8:1.5 plasdone (PVP) is added in solution A, by citric acid Sodium (Na3C6H5O7) be added in aliquots of deionized water, it is configured to solution B；
2) B solution is slowly added to solution A under continuing magnetic force stirring action and forms homogeneous solution C, dropwise into solution C 1.2mol/L N are addedaOH solution Es form solution D, persistently stir 1h afterwards；The volume of solution C and the volume ratio of solution E are 3: 3；
3) it waits for after reaction, solution D being put into hydrothermal reaction kettle and is sealed, is put into homogeneous hydro-thermal reaction instrument, reaction temperature At 180 DEG C, the reaction time controls for 24 hours for degree control；
4) it waits for after reaction, taking out presoma, distinguishes centrifuge washing 2 times through deionized water and absolute ethyl alcohol, obtain white Color presoma, by institute's presoma freeze drier freezing chamber it is subzero 60 DEG C freezing 5h, then vacuum drying cabinet at room temperature Dry 11h obtains nano particle and assembles spherical SnO2Anode material of lithium-ion battery.
Embodiment 3
A kind of spherical SnO of nano particle assembling2The preparation method of anode material of lithium-ion battery, includes the following steps：
1) by SnCl4·5H2O is dissolved in deionized water, is configured to the solution A of a concentration of 1.2mol/L；In mass ratio mSnCl4·5H2O： mPVP：mNa3C6H5O7=1:1.5:1.5 plasdone (PVP) is added in solution A, by citric acid Sodium (Na3C6H5O7) be added in aliquots of deionized water, it is configured to solution B；
2) B solution is slowly added to solution A under continuing magnetic force stirring action and forms homogeneous solution C, dropwise into solution C 0.9mol/L N are addedaOH solution Es form solution D, persistently stir 2h afterwards；The volume of solution C and the volume ratio of solution E are 2: 4；
3) it waits for after reaction, solution D being put into hydrothermal reaction kettle and is sealed, is put into homogeneous hydro-thermal reaction instrument, reaction temperature At 220 DEG C, the reaction time controls in 48h for degree control；
4) it waits for after reaction, taking out presoma, distinguishes centrifuge washing 3 times through deionized water and absolute ethyl alcohol, obtain white Color presoma, by institute's presoma freeze drier freezing chamber it is subzero 60 DEG C freezing 4h, then vacuum drying cabinet at room temperature Dry 12h obtains nano particle and assembles spherical SnO2Anode material of lithium-ion battery.
SnO2Crystal has two kinds of tetragonal crystal system and rhombic system, and wherein orthorhombic phase is unstable, only in high temperature and pressure item The SnO for occurring under part, therefore synthesizing under normal conditions2Crystal belongs to the rutile-type of tetragonal crystal system, cell parameter a= 0.4738nm, c=0.3187nm.Recent studies indicate that SnO2Nano material photocatalysis, gas sensor, transistor, Li-Ion rechargeable battery and solar cell etc. all have stronger application prospect, it is considered to be most have the half of application prospect One of conductor nano material.SnO2The electrode material of base has big (the theoretical reversible capacity 781mAhg of embedding lithium capacity-1), cycle The advantages that performance is good, forthright good again, theoretical reversible capacity is high, and practical reversible capacity is also much larger than commercialization currently on the market The theoretical reversible capacity of various lithium battery carbon negative pole materials.
Since granule-morphology may also can affect to the chemical property of sample, particle is smaller, specific surface Product is bigger, then contact of the material with electrolyte is better, Na+Migration distance can also shorten, be more advantageous to sodium-ion battery in this way The promotion of negative material high rate performance.
A kind of nano particle of the present invention assembles spherical SnO2The preparation method of anode material of lithium-ion battery has and is prepared into The characteristics of this is low, easy to operate, short preparation period, prepared particle assemble spherical SnO2Anode material of lithium-ion battery particle Size only has a few to tens of nanometers, and assembling ball size is about 300~400nm, and purity is high, crystallinity is strong, pattern is uniform, is answered For sodium-ion battery cathode, under the current density of 100mA/g, discharge capacity can reach 409mAh/g, cycle 70 for the first time After secondary, capacity is positively retained at 225.8mAh g-1, there is preferable cyclical stability.

Claims (2)

1. a kind of nano particle assembles spherical SnO2The preparation method of anode material of lithium-ion battery, which is characterized in that including following Step：
1) by SnCl4·5H2O is dissolved in deionized water, is configured to the solution A of a concentration of 0.5mol/L；In mass ratio mSnCl4·5H2O：mPVP：mNa3C6H5O7=1:0.4:0.4 plasdone is added in solution A, sodium citrate is added etc. It measures in deionized water, is configured to solution B；
2) B solution is slowly added to solution A under continuing magnetic force stirring action and forms homogeneous solution C, be added dropwise into solution C 0.3mol/L NaOH solution Es form solution D, persistently stir 0.5h afterwards；The volume of solution C and the volume ratio of solution E are 5:1；
3) it waits for after reaction, solution D being put into hydrothermal reaction kettle and is sealed, is put into homogeneous hydro-thermal reaction instrument, reaction temperature control At 100 DEG C, the reaction time controls in 8h system；
4) it waits for after reaction, taking out presoma, centrifuge washing is distinguished 2 times through deionized water and absolute ethyl alcohol, before obtaining white Body is driven, by institute's presoma in the subzero 50 DEG C of freezings 5h of freezing chamber of freeze drier, is then dried at room temperature in vacuum drying cabinet 10h obtains nano particle and assembles spherical SnO2Anode material of lithium-ion battery；
Nano particle assembles spherical SnO2Anode material of lithium-ion battery assembling ball grain size be 300~400nm, prepared Grain assembles spherical SnO2Anode material of lithium-ion battery is under the current density of 100mA/g, and discharge capacity reaches for the first time 409mAh/g, after recycling 70 times, capacity is maintained at 225.8mAh g-1。
2. a kind of nano particle described in claim 1 assembles spherical SnO2The preparation method of anode material of lithium-ion battery is made Standby nano particle assembles spherical SnO2Anode material of lithium-ion battery.
CN201610049651.9A 2016-01-25 2016-01-25 A kind of spherical SnO of nano particle assembling2Anode material of lithium-ion battery and preparation method thereof Active CN105552351B (en)

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CN105895890A (en) * 2016-06-06 2016-08-24 西北工业大学 Application of Sn3O4 solar catalyst in negative electrode material of lithium ion battery
CN108550842A (en) * 2018-05-18 2018-09-18 天津师范大学 A kind of high specific surface area porous shape stannic oxide anode material of lithium-ion battery of two dimension and preparation method thereof
CN109167019A (en) * 2018-09-03 2019-01-08 大同新成新材料股份有限公司 A kind of cell negative electrode material and preparation method thereof and preparation facilities
CN109378458B (en) * 2018-10-22 2021-09-28 东北大学 Preparation of sodium ion battery negative electrode material ZnS/C-SnO by using tin mud2Method (2)
CN113036113B (en) * 2021-03-11 2022-06-03 东北大学 Doped BaSO4Sodium ion battery cathode material and preparation method thereof

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