CN105390675B - Sodium-ion battery cathode Sn/SnO2The preparation method of/C composite - Google Patents

Sodium-ion battery cathode Sn/SnO2The preparation method of/C composite Download PDF

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CN105390675B
CN105390675B CN201510717866.9A CN201510717866A CN105390675B CN 105390675 B CN105390675 B CN 105390675B CN 201510717866 A CN201510717866 A CN 201510717866A CN 105390675 B CN105390675 B CN 105390675B
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composite
sodium
ion battery
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CN105390675A (en
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黄剑锋
程娅伊
李嘉胤
许占位
曹丽云
欧阳海波
齐慧
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • 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 present invention provides a kind of sodium-ion battery cathode Sn/SnO2The preparation method of/C composite：Using water as solvent, with SnCl2·2H2O uses hydro-thermal calcination method to be prepared for grain size as 0.5~2 μm of Sn/SnO as tin source, glucose as carbon source2/ C composite is assembled into sodium-ion battery using it as negative material, shows excellent chemical property；The carbon source that the present invention uses is of low cost, and preparation method is simple, reaction temperature is low, it is repeated it is high, the period is short, low energy consumption, the needs for being suitble to large-scale production to prepare, and there is significant scientific meaning in sodium-ion battery application aspect.

Description

Sodium-ion battery cathode Sn/SnO2The preparation method of/C composite
Technical field
The present invention relates to a kind of sodium-ion battery cathode SnO2A kind of preparation of based composites, and in particular to sodium ion Battery cathode Sn/SnO2The preparation method of/C composite.
Background technology
Sodium-ion battery is pollution-free since sodium is resourceful, it is safe the advantages that become most possible and substitute lithium ion The secondary cell of battery.Currently, the negative material of sodium-ion battery, carbon based negative electrodes material and titanium-based negative material all have preferably Cyclical stability, but capacity only has 200~300mAh g-1.And due to its limited active site, capacity has been difficult to very Big raising leads to not continue to meet the needs of market is for high energy density cells.Therefore, developing novel has Gao Rong The negative material of amount is meaningful.In the research to negative material, SnO is found2Storage sodium capacity be 1378mAh g-1, much More than the theoretical capacity of graphite and titanium-based negative material, the extensive concern of battery material circle is caused.
However, SnO2With prodigious bulk effect, electrode material is made to be easy powder of detached, performance in charge and discharge process Go out poor cyclical stability.And its special embedding sodium mechanism leads to SnO2Have when as anode material of lithium-ion battery higher Irreversible capacity for the first time, it reduce the efficiency of battery, greatly affected the practical application of this kind of material.At present with carbon or The compound of other substances of person is that the most common type improves SnO2The method of chemical property.Multi-walled carbon nanotube, graphene etc. It is proved to and SnO2It is compound to show preferable cyclical stability (SnO2@MWCNT nanocomposite as a high capacity anode material for sodium-ion batteries.Electrochemistry Communications.2013；29:8-11.SnO2@graphene nanocomposites as anode materials for Na-ion batteries with superior electrochemical performance.Chemical Communications. 2013；49:3131-3133).But these carbon source preparation process are more complicated and expensive, are unfavorable for Use of large-scale production.The SnO that Wu Xuehang etc. are prepared using hydro-thermal-calcine technology2-Fe2O3Composite material exhibits go out Preferable cyclical stability, 30 times cycle after capacity may remain in 313mAh g-1, but coulombic efficiency only has 38% for the first time (Synthesis and electrochemical performance of SnO2–Fe2O3composite as an anode material for Na-ion and Li-ion batteries.Powder Technology.2015；280:119-123). The SnSb-SnO that Kim Jae-Chan etc. are prepared using method of electrostatic spinning2/ Sn/C composite materials, discharge capacity is 841mAh for the first time g-1, but it is only 47% that corresponding coulombic efficiency for the first time, which is, and reversible capacity is maintained at 305mA h g after 40 cycles-1 (Synthesis of multiphase SnSb nanoparticles-on-SnO2/Sn/C nanofibers for use in Li and Na ion battery electrodes. Electrochemistry Communications.2014；46: 124-127).Although with other materials such as Fe2O3, the compound of SnSb etc. being capable of a degree of improvement SnO2Base negative material Cyclical stability, but its low problem of coulombic efficiency is not improved (less than 50%) still for the first time, therefore develop a kind of SnO can be improved2The negative material that the cyclical stability of base negative material can reduce irreversible capacity again has science meaning very much Justice.
Invention content
The purpose of the present invention is to provide a kind of sodium-ion battery cathode Sn/SnO2The preparation method of/C composite.
In order to achieve the above objectives, present invention employs following technical schemes：
1) by 0.524~4.192g SnCl2·2H2O is added in 20~80mL deionized waters, stirring to SnCl2·2H2O Solution is obtained after being completely dissolved, 0.835~3.34g glucose is added into solution, is then ultrasonically treated 10~30min, is made grape Sugar and Sn2+Fully effect obtains uniform mixed liquor；
2) mixed liquor is transferred to after polytetrafluoroethylene (PTFE) water heating kettle and the polytetrafluoroethylene (PTFE) water heating kettle is placed in homogeneous reaction In device, 12~36h is then reacted at 160~220 DEG C, cooled to room temperature, then passes through centrifugation after reaction Precipitation (brown) obtained by the reaction, SnO is obtained by isolated precipitation vacuum freeze drying2/ C powders；
3) by SnO2/ C powders are placed in the vacuum tube furnace full of argon gas, and certainly with the heating rate of 5~30 DEG C/min Room temperature keeps the temperature 3~8h after rising to 600~850 DEG C, and cooled to room temperature after heat preservation obtains Sn/SnO2/ C composite.
The ultrasonic power used that is ultrasonically treated is 50~100W.
Sn in the mixed liquor2+A concentration of 0.03~0.93molL-1。
The SnCl2·2H2The mass ratio of O and glucose is 0.16~5:1.
The compactedness of the water heating kettle is controlled 20~80%.
The condition of the vacuum freeze drying is：- 50 DEG C, 20Pa and 8~12h.
The Sn/SnO2The mass fraction of C is 10~30% in/C composite.
The Sn/SnO2The grain size of/C composite is 0.5~2 μm, and Sn and SnO2Particle is dispersed in carbon base body In.
Beneficial effects of the present invention are embodied in：
The present invention is using water as solvent, with SnCl2·2H2O is as tin source, and glucose is as carbon source, using hydro-thermal-calcining Method is prepared for the Sn/SnO that grain size is 0.5~2 μm2/ C composite is assembled into sodium-ion battery using it as negative material, by In SnO2With higher theoretical capacity, but its irreversible capacity is bigger for the first time, the introducing of Sn, which can reduce, for the first time can not Inverse capacity, while carbon can alleviate the volume expansion of the two as matrix again.Therefore Sn/SnO2/ C composite show compared with Good chemical property.In addition, the carbon source that the present invention uses is of low cost, preparation method is simple, and reaction temperature is low, repeated Height, the period is short, low energy consumption, the needs for being suitble to large-scale production to prepare, and has significant section in sodium-ion battery application aspect Learn meaning.
Description of the drawings
Fig. 1 is the Sn/SnO prepared by embodiment 22X-ray diffraction (XRD) collection of illustrative plates of/C composite；
Fig. 2 is the Sn/SnO prepared by embodiment 22Scanning electron microscope (SEM) photo of/C composite；
Fig. 3 is the Sn/SnO prepared by embodiment 22Transmission electron microscope (TEM) photo of/C composite；
Fig. 4 is the Sn/SnO prepared by embodiment 22The cycle performance figure of/C composite；Wherein, Cycle number： Cycle-index；Capacity：Capacity.
Specific implementation mode
It elaborates with reference to the accompanying drawings and examples to the present invention.
Prepare Sn/SnO2Composite material is a kind of method that can effectively improve reversible capacity, because the introducing of Sn can To improve the Sn in cathode matrix:Na2O ratios reduce irreversible capacity for the first time.And the addition of carbon, it can be used as buffering matrix, delayed Solve Sn, SnO2In the volume expansion of charge and discharge process, to improve cyclical stability.Therefore, Sn/SnO2/ C composite material conducts Anode material of lithium-ion battery has prodigious development and application space.
Embodiment 1
1) by 0.524g SnCl2·2H2O is added in 20mL deionized waters, stirring to SnCl2·2H2O is obtained after being completely dissolved 0.835g glucose is added into solution for solution, is then ultrasonically treated 10min (ultrasonic power 100W), is uniformly mixed Liquid is closed, Sn in mixed liquor2+A concentration of 0.12molL-1；
2) mixed liquor is transferred to after polytetrafluoroethylene (PTFE) water heating kettle and the polytetrafluoroethylene (PTFE) water heating kettle is placed in homogeneous reaction In device (Yantai Ke Li Chemical Equipment Co., Ltd.s, KLJX-8A), then compactedness 20% reacts 28h, instead at 160 DEG C Then cooled to room temperature after answering is precipitated by centrifuging, by isolated precipitation vacuum freeze drying (- 50 DEG C, 20Pa, about 8h) obtain SnO2/ C powders；
3) by SnO2/ C powders are placed in vacuum tube furnace (Hefei Ke Jing Materials Technology Ltd., OTF- full of argon gas In 1200X), heated up from room temperature with the rate of 10 DEG C/min, and 8h is kept the temperature at a temperature of 600 DEG C, it is naturally cold after heat preservation But to room temperature, the Sn/SnO that collects2The compound powders of/C；
4) Rigaku D/max2000PCX- x ray diffractometer xs analysis sample (Sn/SnO is used2The compound powders of/C), it finds The SnO for the tetragonal crystal system that sample is 71-0652 with JCPDS numbers2It is consistent with the Sn structures that JCPDS numbers are 65-2631, but It is that the peak of not carbon occurs, it may be possible to since the peak of carbon is weaker or by SnO2Sharp peak is covered with Sn；By the sample It is observed with the field emission scanning electron microscope (FESEM) of FEI Co. of U.S. S-4800 types, it can be seen that prepared Sn/SnO2/ C composite is the spherical particle of 0.5~2 μm of grain size；Further pass through FEI Co. of U.S. TecnaiG2F20S- The Flied emission transmission electron microscope of TWIN types is observed, it can be seen that the Sn and SnO of Nano grade2It is dispersed in carbon base body In；By XRD refine technology and TG/DSC test analysis, Sn/SnO2The mass fraction of C is 23% in/C composite；
5) with prepared Sn/SnO2The compound powders of/C are assembled into battery as anode material of lithium-ion battery.It uses BTS battery charging and discharging testers test its charge-discharge performance, it can be seen that Sn/SnO2/ C composite is negative as sodium-ion battery When the material of pole, compared to SnO2Its cyclical stability of/C and Sn/C composite materials increases, and capacity is protected after 100 cycles It holds in 200mAh/g, meanwhile, coulombic efficiency is up to 59% for the first time.
Embodiment 2
1) by 1.048g SnCl2·2H2O is added in 50mL deionized waters, stirring to SnCl2·2H2O is obtained after being completely dissolved 1.67g glucose is added into solution for solution, is then ultrasonically treated 20min (ultrasonic power 100W), is uniformly mixed Liquid, Sn in mixed liquor2+A concentration of 0.093molL-1；
2) mixed liquor is transferred to after polytetrafluoroethylene (PTFE) water heating kettle and the polytetrafluoroethylene (PTFE) water heating kettle is placed in homogeneous reaction In device (Yantai Ke Li Chemical Equipment Co., Ltd.s, KLJX-8A), then compactedness 50% is reacted for 24 hours, instead at 180 DEG C Then cooled to room temperature after answering is precipitated by centrifuging, by isolated precipitation vacuum freeze drying (- 50 DEG C, 20Pa, about 10h) obtain SnO2/ C powders；
3) by SnO2/ C powders are placed in vacuum tube furnace (Hefei Ke Jing Materials Technology Ltd., OTF- full of argon gas In 1200X), heated up from room temperature with the rate of 5 DEG C/min, and 5h is kept the temperature at a temperature of 700 DEG C, it is naturally cold after heat preservation But to room temperature, the Sn/SnO that collects2The compound powders of/C；
4) Rigaku D/max2000PCX- x ray diffractometer xs analysis sample (Sn/SnO is used2The compound powders of/C), it finds The SnO for the tetragonal crystal system that sample is 71-0652 with JCPDS numbers2It is consistent with the Sn structures that JCPDS numbers are 65-2631, but It is that the peak of not carbon occurs, it may be possible to since the peak of carbon is weaker or by SnO2Sharp peak is covered with Sn, referring to Fig. 1； The field emission scanning electron microscope (FESEM) of sample FEI Co. of U.S. S-4800 types is observed, it can be seen that Prepared Sn/SnO2/ C composite is the spherical particle of 0.5~2 μm of grain size, referring to Fig. 2；Further pass through U.S. FEI public affairs Department TecnaiG2F20S-TWIN types Flied emission transmission electron microscope observed, it can be seen that the Sn of Nano grade and SnO2It is dispersed in carbon base body, referring to Fig. 3；By XRD refine technology and TG/DSC test analysis, Sn/SnO2/ C composite The mass fraction of middle C is 24%；
5) with prepared Sn/SnO2The compound powders of/C are assembled into battery as anode material of lithium-ion battery.It uses BTS battery charging and discharging testers test its charge-discharge performance, it can be seen that Sn/SnO2/ C composite is negative as sodium-ion battery Preferable chemical property is shown when the material of pole, compared to SnO2/ C and Sn/C composite materials its cyclical stabilities is It improving, capacity is maintained at 200mAh/g after 100 cycles, referring to Fig. 4, meanwhile, coulombic efficiency is up to 59% for the first time.
Embodiment 3
1) by 2.096g SnCl2·2H2O is added in 50mL deionized waters, stirring to SnCl2·2H2O is obtained after being completely dissolved 1.67g glucose is added into solution for solution, is then ultrasonically treated 20min (ultrasonic power 100W), is uniformly mixed Liquid, Sn in mixed liquor2+A concentration of 0.186molL-1；
2) mixed liquor is transferred to after polytetrafluoroethylene (PTFE) water heating kettle and the polytetrafluoroethylene (PTFE) water heating kettle is placed in homogeneous reaction In device (Yantai Ke Li Chemical Equipment Co., Ltd.s, KLJX-8A), then compactedness 50% is reacted for 24 hours, instead at 180 DEG C Then cooled to room temperature after answering is precipitated by centrifuging, by isolated precipitation vacuum freeze drying (- 50 DEG C, 20Pa, about 10h) obtain SnO2/ C powders；
3) by SnO2/ C powders are placed in vacuum tube furnace (Hefei Ke Jing Materials Technology Ltd., OTF- full of argon gas In 1200X), heated up from room temperature with the rate of 20 DEG C/min, and 6h is kept the temperature at a temperature of 800 DEG C, it is naturally cold after heat preservation But to room temperature, the Sn/SnO that collects2The compound powders of/C；
4) Rigaku D/max2000PCX- x ray diffractometer xs analysis sample (Sn/SnO is used2The compound powders of/C), it finds The SnO for the tetragonal crystal system that sample is 71-0652 with JCPDS numbers2It is consistent with the Sn structures that JCPDS numbers are 65-2631, but It is that the peak of not carbon occurs, it may be possible to since the peak of carbon is weaker or by SnO2Sharp peak is covered with Sn；By the sample It is observed with the field emission scanning electron microscope (FESEM) of FEI Co. of U.S. S-4800 types, it can be seen that prepared Sn/SnO2/ C composite is the spherical particle of 0.5~2 μm of grain size；Further pass through FEI Co. of U.S. TecnaiG2F20S- The Flied emission transmission electron microscope of TWIN types is observed, it can be seen that the Sn and SnO of Nano grade2It is dispersed in carbon base body In；By XRD refine technology and TG/DSC test analysis, Sn/SnO2The mass fraction of C is 13% in/C composite；
5) with prepared Sn/SnO2The compound powders of/C are assembled into battery as anode material of lithium-ion battery.It uses BTS battery charging and discharging testers test its charge-discharge performance, it can be seen that Sn/SnO2/ C composite is negative as sodium-ion battery Preferable chemical property is shown when the material of pole, compared to SnO2/ C and Sn/C composite materials its cyclical stabilities is It improving, capacity is maintained at 200mAh/g after 100 cycles, meanwhile, coulombic efficiency is up to 59% for the first time.
Embodiment 4
1) by 4.192g SnCl2·2H2O is added in 80mL deionized waters, stirring to SnCl2·2H2O is obtained after being completely dissolved 3.34g glucose is added into solution for solution, is then ultrasonically treated 30min (ultrasonic power 100W), is uniformly mixed Liquid, Sn in mixed liquor2+A concentration of 0.23molL-1；
2) mixed liquor is transferred to after polytetrafluoroethylene (PTFE) water heating kettle and the polytetrafluoroethylene (PTFE) water heating kettle is placed in homogeneous reaction In device (Yantai Ke Li Chemical Equipment Co., Ltd.s, KLJX-8A), then compactedness 80% is reacted for 24 hours, instead at 200 DEG C Then cooled to room temperature after answering is precipitated by centrifuging, by isolated precipitation vacuum freeze drying (- 50 DEG C, 20Pa, about 12h) obtain SnO2/ C powders；
3) by SnO2/ C powders are placed in vacuum tube furnace (Hefei Ke Jing Materials Technology Ltd., OTF- full of argon gas In 1200X), heated up from room temperature with the rate of 10 DEG C/min, and 8h is kept the temperature at a temperature of 700 DEG C, it is naturally cold after heat preservation But to room temperature, the Sn/SnO that collects2The compound powders of/C；
4) Rigaku D/max2000PCX- x ray diffractometer xs analysis sample (Sn/SnO is used2The compound powders of/C), it finds The SnO for the tetragonal crystal system that sample is 71-0652 with JCPDS numbers2It is consistent with the Sn structures that JCPDS numbers are 65-2631, but It is that the peak of not carbon occurs, it may be possible to since the peak of carbon is weaker or by SnO2Sharp peak is covered with Sn；By the sample It is observed with the field emission scanning electron microscope (FESEM) of FEI Co. of U.S. S-4800 types, it can be seen that prepared Sn/SnO2/ C composite is the spherical particle of 0.5~2 μm of grain size；Further pass through FEI Co. of U.S. TecnaiG2F20S- The Flied emission transmission electron microscope of TWIN types is observed, it can be seen that the Sn and SnO of Nano grade2It is dispersed in carbon base body In；By XRD refine technology and TG/DSC test analysis, Sn/SnO2The mass fraction of C is 15% in/C composite；
5) with prepared Sn/SnO2The compound powders of/C are assembled into battery as anode material of lithium-ion battery.It uses BTS battery charging and discharging testers test its charge-discharge performance, it can be seen that Sn/SnO2/ C composite is negative as sodium-ion battery Preferable chemical property is shown when the material of pole, compared to SnO2/ C and Sn/C composite materials its cyclical stabilities is It improves, capacity is maintained at 200mAh/g after 100 cycles.Meanwhile for the first time coulombic efficiency up to 59%.
Embodiment 5
1) by 2.096g SnCl2·2H2O is added in 50mL deionized waters, stirring to SnCl2·2H2O is obtained after being completely dissolved 3.34g glucose is added into solution for solution, is then ultrasonically treated 25min (ultrasonic power 100W), is uniformly mixed Liquid, Sn in mixed liquor2+A concentration of 0.186molL-1；
2) mixed liquor is transferred to after polytetrafluoroethylene (PTFE) water heating kettle and the polytetrafluoroethylene (PTFE) water heating kettle is placed in homogeneous reaction In device (Yantai Ke Li Chemical Equipment Co., Ltd.s, KLJX-8A), then compactedness 50% reacts 28h, instead at 180 DEG C Then cooled to room temperature after answering is precipitated by centrifuging, by isolated precipitation vacuum freeze drying (- 50 DEG C, 20Pa, about 12h) obtain SnO2/ C powders；
3) by SnO2/ C powders are placed in vacuum tube furnace (Hefei Ke Jing Materials Technology Ltd., OTF- full of argon gas In 1200X), heated up from room temperature with the rate of 5 DEG C/min, and 6h, natural cooling after heat preservation are kept the temperature at a temperature of 750 DEG C To room temperature, the Sn/SnO that collects2The compound powders of/C；
4) Rigaku D/max2000PCX- x ray diffractometer xs analysis sample (Sn/SnO is used2The compound powders of/C), it finds The SnO for the tetragonal crystal system that sample is 71-0652 with JCPDS numbers2It is consistent with the Sn structures that JCPDS numbers are 65-2631, but It is that the peak of not carbon occurs, it may be possible to since the peak of carbon is weaker or by SnO2Sharp peak is covered with Sn；By the sample It is observed with the field emission scanning electron microscope (FESEM) of FEI Co. of U.S. S-4800 types, it can be seen that prepared Sn/SnO2/ C composite is the spherical particle of 0.5~2 μm of grain size；Further pass through FEI Co. of U.S. TecnaiG2F20S- The Flied emission transmission electron microscope of TWIN types is observed, it can be seen that the Sn and SnO of Nano grade2It is dispersed in carbon base body In；By XRD refine technology and TG/DSC test analysis, Sn/SnO2The mass fraction of C is 25% in/C composite；
5) with prepared Sn/SnO2The compound powders of/C are assembled into battery as anode material of lithium-ion battery.It uses BTS battery charging and discharging testers test its charge-discharge performance, it can be seen that Sn/SnO2/ C composite is negative as sodium-ion battery Preferable chemical property is shown when the material of pole, compared to SnO2/ C and Sn/C composite materials its cyclical stabilities is It improving, capacity is maintained at 200mAh/g after 100 cycles, meanwhile, coulombic efficiency is up to 59% for the first time.
In short, the present invention is using water as solvent, using glucose as carbon source, use hydrothermal-sintering process be prepared for grain size for 0.5~2 μm of Sn/SnO2/ C composite is assembled into sodium-ion battery using it as negative material, shows excellent electricity Chemical property；The carbon source that the present invention uses is of low cost, and preparation method is simple, reaction temperature is low, it is repeated it is high, the period is short, energy The needs low, large-scale production is suitble to prepare are consumed, and there is significant scientific meaning in sodium-ion battery application aspect.

Claims (6)

1. a kind of sodium-ion battery cathode Sn/SnO2The preparation method of/C composite, it is characterised in that：Include the following steps：
1) by 0.524~4.192g SnCl2·2H2O is added in 20~80mL deionized waters, stirring to SnCl2·2H2O is completely molten Solution is obtained after solution, 0.835~3.34g glucose is added into solution, is then ultrasonically treated 10~30min, is obtained mixed liquor；
2) mixed liquor is transferred to after polytetrafluoroethylene (PTFE) water heating kettle and the polytetrafluoroethylene (PTFE) water heating kettle is placed in homogeneous reactor, Then 24~36h is reacted at 160~220 DEG C, after reaction cooled to room temperature, then reacted by centrifuging Isolated precipitation vacuum freeze drying is obtained SnO by the precipitation arrived2/ C powders；
3) by SnO2/ C powders are placed in the vacuum tube furnace full of argon gas, and with the heating rate of 5~30 DEG C/min from room temperature liter 5~8h is kept the temperature after to 600~850 DEG C, cooled to room temperature after heat preservation obtains Sn/SnO2/ C composite；
The Sn/SnO2The mass fraction of C is 10~30% in/C composite；
The Sn/SnO2The grain size of/C composite is 0.5~2 μm, and Sn and SnO2Particle is dispersed in carbon base body.
2. a kind of sodium-ion battery cathode Sn/SnO according to claim 12The preparation method of/C composite, feature It is：The ultrasonic power used that is ultrasonically treated is 50~100W.
3. a kind of sodium-ion battery cathode Sn/SnO according to claim 12The preparation method of/C composite, feature It is：Sn in the mixed liquor2+A concentration of 0.03~0.93molL-1。
4. a kind of sodium-ion battery cathode Sn/SnO according to claim 12The preparation method of/C composite, feature It is：The SnCl2·2H2The mass ratio of O and glucose is 0.16~5:1.
5. a kind of sodium-ion battery cathode Sn/SnO according to claim 12The preparation method of/C composite, feature It is：The compactedness of the water heating kettle is controlled 20~80%.
6. a kind of sodium-ion battery cathode Sn/SnO according to claim 12The preparation method of/C composite, feature It is：The condition of the vacuum freeze drying is：- 50 DEG C, 20Pa and 8~12h.
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CN106099052A (en) * 2016-07-23 2016-11-09 合肥工业大学 A kind of carbon cladding SnO2hollow nanospheres composite and preparation method thereof
CN107069004B (en) * 2017-04-11 2019-10-11 东南大学 A kind of preparation method of the lithium ion battery negative material of three-dimensional porous structure
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