CN109786684A - A kind of porous Sn of high-performance3O4Base carbon composite and its preparation method and application - Google Patents
A kind of porous Sn of high-performance3O4Base carbon composite and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of porous Sn of high-performance3O4Base carbon composite and its preparation method and application, by using commercialized micron-sized SnO as starting material, add P@F-127, silica dioxide gel in aqueous solution, pass through sufficient ultrasonic mixing, aniline monomer is dispersed therein, ammonium persulfate initiated polymerization is added under condition of ice bath, passes through Ar/H after the product after reaction is dried via washing2Gaseous mixture heat treatment removes silica finally by hydrofluoric acid aqueous solution, the porous Sn of high-performance is prepared3O4Base carbon composite.The invention also discloses the porous Sn of the high-performance3O4Base carbon composite and its application.The characteristics of present invention is according to bulk effect is prone in lithium battery and sode cell negative electrode material charge and discharge cycles, using cheap commercialization micron order SnO as starting material, micron order SnO is re-assemblied by ultrasound and high temperature and is dispersed into nanoscale Sn3O4Material, and be well-dispersed in and mixed inside porous carbon materials rich in hetero atom.
Description
Technical field
The present invention relates to lithium/anode material of lithium-ion battery technical fields, and in particular to a kind of porous Sn of high-performance3O4Base
Carbon composite and its preparation method and application.
Background technique
Lithium ion battery have open-circuit voltage is high, energy density is big, long service life, memoryless effect, of low pollution and
The advantages that self-discharge rate is small, it is better than other traditional secondary batteries on overall performance, is unanimously considered as various portable electrics
Sub- equipment and ideal power supply for electric vehicle.Although conventional lithium ion battery negative electrode material graphite good cycling stability with
And sexual valence is relatively high, but since its charging and discharging capacity is lower, volume and capacity ratio is even more no advantage, it is difficult to meet dynamical system
The system especially requirement of electric vehicle and hybrid electric vehicle to cell high-capacity.Therefore exploitation has height ratio capacity, high charge-discharge
Efficiency, the great urgency of novel cathode material for lithium ion battery of long circulation life.
In numerous tin-oxides, Sn3O4With very high theoretical lithium storage content (twice of graphite), as lithium-ion electric
Pond negative electrode material can effectively improve the energy density of lithium ion battery, while its safety is good, resources reserve amount is abundant, is most
One of the lithium ion battery negative material instead of graphite of development potentiality.However the main problem of its practical application is hindered at present
It is that it has biggish volume change (300%) during cycle charge-discharge, negative electrode material is easy dusting, leads to cycle performance
Poor, in addition, there is also the common problems of poorly conductive for this quasi-metal oxides, this is also a weight for influencing its practical application
Want factor.
Currently, tin monoxide material has been able to achieve large-scale production.However since its partial size is larger (micron order),
It is in battery material in application, cycle performance and high rate performance are poor.How the application range of commercialization tin monoxide is expanded,
Have become the bottleneck for restricting its development.
Summary of the invention
For the deficiency of existing issue, the first purpose of the invention is to provide a kind of porous Sn of high-performance3O4Base carbon is compound
The preparation method of material；
A second object of the present invention is to provide a kind of porous Sn of high-performance3O4Base carbon composite；
Third object of the present invention is to provide a kind of porous Sn of high-performance3O4Base carbon composite is in lithium ion battery side
The application in face.
The technical solution used to solve the technical problems of the present invention is that:
A kind of porous Sn of high-performance3O4The preparation method of base carbon composite passes through the nanometer anode material table in high capacity
Face introduces SiO2Layer is used as sacrificial layer, by adding P@F-127, dioxy using commercialized micron-sized SnO as starting material
Aniline monomer is dispersed therein by SiClx gel in aqueous solution and by sufficient ultrasonic mixing, is added under condition of ice bath
Ammonium persulfate initiated polymerization passes through Ar/H after drying the product after reaction via washing2Gaseous mixture heat treatment, finally leads to
Hydrofluoric acid aqueous solution removal silica is crossed, the porous Sn of high-performance is prepared3O4Base carbon composite.
Further, the preparation method specifically includes the following steps:
(1) P@F-127 is taken to be scattered in deionized water, ultrasonic agitation is until be completely dissolved, then take silica dioxide gel molten
In wherein, it is stirred by ultrasonic 20 minutes, makes it completely dissolved；
(2) commercialization SnO is added in step (1) solution, ultrasound makes it be uniformly dispersed, aniline monomer is then added dropwise, and surpasses
Sound is dispersed with stirring uniformly, and above-mentioned solution is transferred in round-bottomed flask, is stirred 20 minutes under condition of ice bath；Concentrated hydrochloric acid is added dropwise,
Continue to stir under condition of ice bath；
(3) prepare the aqueous solution containing ammonium persulfate, by addition above-mentioned steps (2) solution in；Keep condition of ice bath, stirring
React 12h；It filters after reaction, washing three times, is dried in vacuo；
(4) by the composite material of step (3) in Ar/H2High-temperature process under gaseous mixture, then handled with dilute HF acid and answered up to this
Condensation material.
The particle diameter of the SnO is 5~50 μm；Its particle size range of the silica dioxide gel is 5~40nm, with water
Mass ratio be 0.5:100~5:100；The mass ratio of the SnO and water is 0.1:100~1:100；The P@F-127, with
The mass ratio of water is 0.1:100~1:100；The concentrated hydrochloric acid, aniline, substance withdrawl syndrome range is respectively 0.01~
0.24mM/mL, 0.01~0.22mM/mL；The aqueous solution of the ammonium persulfate, the additional amount of ammonium persulfate are aniline monomer
1.5~3 times of quality.
Further, the high-temperature process condition is 400~700 DEG C of 0.5~6h.
Further, the dosage of the HF acid is 5~30%, and the processing time is 0.5~12h.
Further, the porous structure is mesoporous carbon, and hollow interporal lacuna is 5-40nm.
Further, the porous Sn3O4Carbon and Sn in the preparation method of base carbon composite3O4Mass ratio be 1:5
~1:1 can play carbon under the ratio and improve conductivity, the contribution for inhibiting volume expansion and institute in the composite
The combination electrode of preparation specific capacity with higher.
The porous Sn of the high-performance that above-mentioned preparation method is prepared3O4Base carbon composite.
The porous Sn of above-mentioned high-performance3O4Application of the base carbon composite in terms of preparing combination electrode.
Beneficial effect
The present invention is according to the feature in lithium cell cathode material charge and discharge cycles, with commercialized micron-sized SnO
Beginning raw material, one-step method preparation mix porous carbon-nanometer Sn rich in hetero atom3O4Composite material.The composite construction is conducive to the biography of electronics
It leads and the quick diffusion of lithium electrolyte, can significantly improve the spies such as commercialization micron order SnO decaying is fast, reversible capacity is low
Point adapts to the negative electrode material for being used for power battery material.
The present invention prepares environmental protection, and operating procedure is simple, high income, and the charge-discharge performance of material is excellent, convenient for industrial metaplasia
It produces.
Detailed description of the invention
Fig. 1 is the XRD diagram of sample prepared by Examples 1 to 4, wherein a, b, c, d corresponding embodiment 1-4；
Fig. 2 is the SEM photograph of sample prepared by Examples 1 to 4: (a) commercialization SnO material, (b) sample of embodiment 1,
(c/d) sample of embodiment 2 is (e) sample of embodiment 3, (f) is the sample of embodiment 4；
Fig. 3 is electrode of lithium cell prepared by composite material prepared by Examples 1 to 4 in 500mAg-1Charging and discharging currents
Cycle performance test curve under density, wherein a, b, c, d corresponding embodiment 1-4；
Fig. 4 is that embodiment 2 prepares sodium-ion battery electrode prepared by composite material and related electrode in 1Ag-1Fill
Cycle performance test curve under discharge current density.
Specific embodiment
The present invention is described in further details with reference to embodiments.Production is not specified in agents useful for same or instrument and equipment
Manufacturer, it is accordingly to be regarded as the conventional products that can be bought by market.
Embodiment 1
0.5g P@F-127 is taken to be scattered in 100mL deionized water, ultrasonic agitation is until be completely dissolved, then take 0.5g dioxy
SiClx gel (40nm) is dissolved in wherein, is stirred by ultrasonic 20 minutes, is made it completely dissolved；Commercialization SnO (the 5- of 0.5g is then added
50 μm), ultrasonic 1h makes it be uniformly dispersed, and 0.4mL aniline monomer is then added dropwise, and ultrasonic agitation is uniformly dispersed, and above-mentioned solution is turned
It moves in round-bottomed flask, is stirred 20 minutes under condition of ice bath, 0.5mL concentrated hydrochloric acid is added, continue ice-water bath stirring.In addition it prepares
10mL (NH containing 1g4)2S2O8Aqueous solution, by the above-mentioned mixed solution of addition in.Condition of ice bath is kept, 12h is stirred to react.Instead
It is filtered after answering, three times, vacuum drying obtains composite material for washing.By composite material in Ar/H2High-temperature process under gaseous mixture
500℃6h.5h is handled with dilute 10%HF acid, after being cleaned with a large amount of deionized waters, hollow interporal lacuna is prepared in vacuum drying
For the porous Sn of 40nm or so high-performance3O4Base carbon composite.Porous Sn3O4In the preparation method of base carbon composite carbon with
Sn3O4Mass ratio be 1:3.0.
After sintered material is fully ground and carbon black and carboxymethyl cellulose according to 70: 15: 15 ratio, mixing
Uniformly, 70 DEG C of vacuum drying 4h after film, are prepared combination electrode.It is to electricity with lithium piece by electrode in 2025 battery cases
Pole, using polyethylene film as diaphragm, with 1M LiPF6EC/DEC (v/v=1/1) is that electrolyte assembled battery carries out constant current charge and discharge
Electrical testing.
Embodiment 2
0.3g P@F-127 is taken to be scattered in 100mL deionized water, ultrasonic agitation is until be completely dissolved, then take 1g titanium dioxide
Silica hydrogel (5nm) is dissolved in wherein, is stirred by ultrasonic 20 minutes, is made it completely dissolved；Commercialization SnO (the 10-30 of 0.6g is then added
μm), ultrasonic 1h makes it be uniformly dispersed, and 0.4mL aniline monomer is then added dropwise, and ultrasonic agitation is uniformly dispersed, above-mentioned solution is shifted
It into round-bottomed flask, is stirred 20 minutes under condition of ice bath, 0.5mL concentrated hydrochloric acid is added, continue ice-water bath stirring.In addition it prepares
10mL (NH containing 1.2g4)2S2O8Aqueous solution, by the above-mentioned mixed solution of addition in.Condition of ice bath is kept, 12h is stirred to react.
It filters after reaction, three times, vacuum drying obtains composite material for washing.By composite material in Ar/H2Under gaseous mixture at high temperature
Manage 600 DEG C of 3h.0.5h is handled with dilute 30%HF acid, after being cleaned with a large amount of deionized waters, hollow hole is prepared in vacuum drying
Gap is 5nm or so the porous Sn of high-performance3O4Base carbon composite.Porous Sn3O4In the preparation method of base carbon composite carbon with
Sn3O4Mass ratio be 1:3.3.
After sintered material is fully ground and carbon black and carboxymethyl cellulose according to 70: 15: 15 ratio, mixing
Uniformly, 70 DEG C of vacuum drying 4h after film, are prepared combination electrode.It is to electricity with lithium piece by electrode in 2025 battery cases
Pole, using polyethylene film as diaphragm, with 1M LiPF6EC/DEC (v/v=1/1) is that electrolyte assembled battery carries out constant current charge and discharge
Electrical testing.
After sintered material is fully ground and carbon black and carboxymethyl cellulose according to 70: 15: 15 ratio, mixing
Uniformly, 60 DEG C of vacuum drying 4h after film, are prepared combination electrode.It is to electricity with sodium piece by electrode in 2025 battery cases
Pole, using polyethylene film as diaphragm, with 1M NaClO4It is electrolyte assembling electricity in EC:EMC:DMC (volume ratio 1/1/1)+5%FEC
Pond carries out constant current charge-discharge test.
Embodiment 3
0.1g P@F-127 is taken to be scattered in 100mL deionized water, ultrasonic agitation is until be completely dissolved, then take 0.5g dioxy
SiClx gel (40nm) is dissolved in wherein, is stirred by ultrasonic 20 minutes, is made it completely dissolved；Commercialization SnO (the 5- of 0.1g is then added
50 μm), ultrasonic 1h makes it be uniformly dispersed, and 0.4mL aniline monomer is then added dropwise, and ultrasonic agitation is uniformly dispersed, and above-mentioned solution is turned
It moves in round-bottomed flask, is stirred 20 minutes under condition of ice bath, 0.1mL concentrated hydrochloric acid is added, continue ice-water bath stirring.In addition it prepares
10mL (NH containing 1g4)2S2O8Aqueous solution, by the above-mentioned mixed solution of addition in.Condition of ice bath is kept, 12h is stirred to react.Instead
It is filtered after answering, three times, vacuum drying obtains composite material for washing.By composite material in Ar/H2High-temperature process under gaseous mixture
700℃0.5h.12h is handled with dilute 10%HF acid, after being cleaned with a large amount of deionized waters, hollow hole is prepared in vacuum drying
Gap is 40nm or so the porous Sn of high-performance3O4Base carbon composite.Porous Sn3O4Carbon in the preparation method of base carbon composite
With Sn3O4Mass ratio be 1:1.1.
After sintered material is fully ground and carbon black and carboxymethyl cellulose according to 70: 15: 15 ratio, mixing
Uniformly, 70 DEG C of vacuum drying 4h after film, are prepared combination electrode.It is to electricity with lithium piece by electrode in 2025 battery cases
Pole, using polyethylene film as diaphragm, with 1M LiPF6EC/DEC (v/v=1/1) is that electrolyte assembled battery carries out constant current charge and discharge
Electrical testing.
Embodiment 4
1g P@F-127 is taken to be scattered in 100mL deionized water, ultrasonic agitation is until be completely dissolved, then take 5g silica
Gel (5nm) is dissolved in wherein, is stirred by ultrasonic 20 minutes, is made it completely dissolved；The commercialization SnO (5-50 μm) of 1g is then added,
Ultrasonic 1h, makes it be uniformly dispersed, and 2mL aniline monomer is then added dropwise, and ultrasonic agitation is uniformly dispersed, and above-mentioned solution is transferred to round bottom
It in flask, is stirred 20 minutes under condition of ice bath, 2mL concentrated hydrochloric acid is added, continue ice-water bath stirring.In addition it prepares 10mL and contains 3g
(NH4)2S2O8Aqueous solution, by the above-mentioned mixed solution of addition in.Condition of ice bath is kept, 12h is stirred to react.After reaction
It filters, three times, vacuum drying obtains composite material for washing.By composite material in Ar/H2400 DEG C of 6h of high-temperature process under gaseous mixture.
5h is handled with dilute 10%HF acid, after being cleaned with a large amount of deionized waters, vacuum drying, it is 5nm left that hollow interporal lacuna, which is prepared,
The right porous SnO of high-performancexBase carbon composite.Porous Sn3O4Carbon and Sn in the preparation method of base carbon composite3O4Mass ratio
For 1:4.5.
After sintered material is fully ground and carbon black and carboxymethyl cellulose according to 70: 15: 15 ratio, mixing
Uniformly, 70 DEG C of vacuum drying 4h after film, are prepared combination electrode.It is to electricity with lithium piece by electrode in 2025 battery cases
Pole, using polyethylene film as diaphragm, with 1M LiPF6EC/DEC (v/v=1/1) is that electrolyte assembled battery carries out constant current charge and discharge
Electrical testing.
Material characterization and electrochemical property test
It is mutually tested below by object to the appearance structure of composite material and by cycle performance test prepared by the present invention
The electrochemistry of composite material can be carried out test and characterization.
1.XRD analysis
Fig. 1 is the XRD spectrum of Examples 1 to 4.It can be seen from the chart, sample prepared by Examples 1 to 4 is Sn3O4
Structure.
2, morphology analysis
Fig. 2 is the SEM photograph of sample prepared by Examples 1 to 4: SnO material (a) is commercialized, it can be seen that particle
Chondritic is presented, size is differed from 5~50 μm；(b-f) Examples 1 to 4 sample SEM, can be seen from the chart, prepared
Material surface contain a large amount of empty structures, the spherical SnO of 5~50 μm of structures no longer exists, and obtains being uniform compound
Phase structure.
3, cycle performance is tested
Fig. 3 is electrode of lithium cell prepared by composite negative pole material prepared by Examples 1 to 4 in 500mAg-1Charge and discharge
Cycle performance test curve under current density；It can be seen from the chart, sample prepared by embodiment is used as cathode of lithium battery
Preferable cycle performance is presented, is able to maintain 400mAhg after 100 circulations-1Above reversible capacity, compared to commercialized
SnO and carbon material greatly improve and improve.
Fig. 4 is that embodiment 2 prepares sodium-ion battery electrode prepared by composite negative pole material and related electrode in 1Ag-1
Charging and discharging currents density under cycle performance test curve；It can be seen from the chart, sample prepared by embodiment is used as sodium
Preferable cycle performance is presented in battery cathode, is able to maintain 300mAhg after 100 circulations-1The reversible capacity of left and right, is compared
Commercialized SnO and carbon material greatly improve and improve.
In conclusion present invention realization prepares porous Sn3O4Base carbon composite, prepared material present uniform more
Pore structure, the structure can sufficiently solve stannic oxide materials as lithium/sode cell negative electrode material bulk effect etc. in cyclic process
Polarization can be greatly reduced in problem, greatly improve the cycle performance for improving battery.
Protection content of the invention is not limited to above embodiments.Without departing from the spirit and scope of the invention, originally
Field technical staff it is conceivable that variation and advantage be all included in the present invention, and with the attached claims be protection
Range.
Claims (9)
1. a kind of porous Sn of high-performance3O4The preparation method of base carbon composite, which is characterized in that by by commercialized micron
The SnO of grade is used as starting material, addition P@F-127, silica dioxide gel in aqueous solution and by sufficient ultrasonic mixing,
Aniline monomer is dispersed therein, ammonium persulfate initiated polymerization is added under condition of ice bath, by the product after reaction via washing
Pass through Ar/H after washing drying2Gaseous mixture high-temperature process removes silica finally by hydrofluoric acid aqueous solution, high property is prepared
It can porous Sn3O4Base carbon composite.
2. the porous Sn of a kind of high-performance according to claim 13O4The preparation method of base carbon composite, which is characterized in that
Specifically includes the following steps:
(1) P@F-127 is taken to be scattered in 100 mL deionized waters, ultrasonic agitation is until be completely dissolved, then take silica dioxide gel
It is dissolved in wherein, is stirred by ultrasonic 20 minutes, makes it completely dissolved；
(2) commercialization SnO is added in step (1) solution, 1 h of ultrasound makes it be uniformly dispersed, aniline monomer is then added dropwise, and surpasses
Sound is dispersed with stirring uniformly, and above-mentioned solution is transferred in round-bottomed flask, is stirred 20 minutes under condition of ice bath；Concentrated hydrochloric acid is added dropwise,
Continue to stir under condition of ice bath；
(3) prepare the aqueous solution containing ammonium persulfate, by addition above-mentioned steps (2) solution in；Condition of ice bath is kept, is stirred to react
12 h；It filters after reaction, washing three times, is dried in vacuo；
(4) by the composite material of step (3) in Ar/H2High-temperature process under gaseous mixture, then handled with dilute HF acid up to the composite wood
Material.
3. the porous Sn of a kind of high-performance according to claim 1 or 23O4The preparation method of base carbon composite, feature exist
In the particle diameter of the SnO is 5~50 μm；Its particle size range of the silica dioxide gel is 5~40 nm, with water
Mass ratio be 0.5:100 ~ 5:100；The mass ratio of the SnO and water is 0.1:100 ~ 1:100；The P@F-127, with water
Mass ratio be 0.1:100 ~ 1:100；The concentrated hydrochloric acid, aniline, substance withdrawl syndrome range are respectively 0.01~0.24
MM/mL, 0.01~0.22 mM/mL；The aqueous solution of the ammonium persulfate, the additional amount of ammonium persulfate are the matter of aniline monomer
1.5~3 times of amount.
4. the porous Sn of a kind of high-performance according to claim 1 or 23O4The preparation method of base carbon composite, feature exist
In the high-temperature process condition is 400~700 DEG C of 0.5 ~ 6h.
5. the porous Sn of a kind of high-performance according to claim 1 or 23O4The preparation method of base carbon composite, feature exist
In the dosage of the HF acid is 5~30%, and the processing time is 0.5~12 h.
6. the porous Sn of a kind of high-performance according to claim 1 or 23O4The preparation method of base carbon composite, feature exist
In the porous structure is mesoporous carbon, and hollow interporal lacuna is 5-40 nm.
7. the porous Sn of a kind of high-performance according to claim 1 or 23O4The preparation method of base carbon composite, feature exist
In the porous Sn3O4Carbon and Sn in the preparation method of base carbon composite3O4Mass ratio be 1:5~1:1.
8. the porous Sn of the high-performance that preparation method of any of claims 1 or 2 is prepared3O4Base carbon composite.
9. the porous Sn of high-performance high-performance according to any one of claims 83O4Base carbon composite is preparing lithium ion battery, sodium ion
Application in terms of battery combination electrode.
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| CN104916829A (en) * | 2015-04-20 | 2015-09-16 | 长春理工大学 | Nitrogen-doped porous nanometer carbon-tin composite lithium ion battery negative electrode material and preparation method thereof |
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| EP2991136A1 (en) * | 2014-08-29 | 2016-03-02 | Centre National De La Recherche Scientifique | Method for manufacturing a miniaturized electrochemical cell |
| CN104916829A (en) * | 2015-04-20 | 2015-09-16 | 长春理工大学 | Nitrogen-doped porous nanometer carbon-tin composite lithium ion battery negative electrode material and preparation method thereof |
| CN107369819A (en) * | 2017-07-05 | 2017-11-21 | 合肥国轩高科动力能源有限公司 | Double carbon shell tinbase lithium ion battery negative materials of a kind of egg-shaped and preparation method thereof |
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