CN103346304B - Tin-carbon composite material for lithium secondary battery negative electrode and preparation method thereof - Google Patents
Tin-carbon composite material for lithium secondary battery negative electrode and preparation method thereof Download PDFInfo
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- CN103346304B CN103346304B CN201310254088.5A CN201310254088A CN103346304B CN 103346304 B CN103346304 B CN 103346304B CN 201310254088 A CN201310254088 A CN 201310254088A CN 103346304 B CN103346304 B CN 103346304B
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract
The invention relates to a tin-carbon composite material for a lithium secondary battery negative electrode. The tin-carbon composite material is in a three-dimensional porous structure which is formed by uniformly dispersing the tin nano particles with ultrasmall granularity and embedding the tin nano particles into a three-dimensional porous carbon carrier material. The preparation method comprises the following steps of: utilizing a high-temperature pyrolysis tin compound, and uniformly dispersing and embedding the tin nano particles with ultrasmall granularity into the three-dimensional porous carbon carrier material. The high specific capacity characteristic of the tin can be maintained, the volume expansion of an electrode can be effectively controlled, the agglomeration phenomenon of the particles can be prevented, and the cycling stability can be improved; and the tin-carbon composite material can be used for preparing a lithium-ion battery. The tin-carbon composite material and the preparation method have the advantages that the ultrasmall granularity of the composite material and the three-dimensional porous structure favors the fast transmission of the ions, so that the power density of the lithium secondary battery negative material can be improved, and the cycling stability and magnification performance are good; and the preparation process is easy to control and simple to operate, the industrialized mass production is convenient to realize, and the tin-carbon composite material is expected to be applied to the next generation of high-energy high-power environment-friendly storage battery.
Description
Technical field
The present invention relates to tin carbon composite and preparation method thereof and application, particularly a kind of tin carbon composite for lithium secondary battery anode and preparation method thereof.
Background technology
Along with the electrical source of power such as electric automobile are to the eager demand of electrical power storage, energy and the power density of lithium ion battery Yin Qigao are more and more barred up.The negative material of current business-like lithium ion battery is graphite, its low theoretical capacity (372 mAh/g) can not meet the pursuit of people for high-energy and high power density, this will ask for help develop the Novel anode material with high power capacity, high cyclical stability and high rate capability.Metal simple-substance tin has high theoretical specific capacity (992 mAh/g), low intercalation potential, is considered to one of the most promising negative material of lithium ion battery of future generation.But tin with large change in volume, can cause the efflorescence of particle and the disengaging of active material and collector, causes the sharply decline of capacity in charge and discharge process.On the other hand, due to tin change in volume repeatedly in cyclic process, can make electrode material and electrolyte interface react and generate solid electrolyte circle Mian Mo (SEI film) breaking and generating repeatedly, constantly consume electrolyte so that finally affect the cycle life of battery.These all seriously limit the application of tin negative pole material.
The size of tin negative pole material is reduced to nanoscale and can reduces to take off/embedding lithium process in the stress that produces, prevent breaking and efflorescence of material, see: J. Besenhard, J. Yang, M. Winter, Will advanced lithium-alloy anodes have a chance in lithium-ion batteries.
journal of Power Sources, 1997,68:87.Nanometer can also reduce the transmission path of lithium ion, improves high rate performance.But nano particle can be reunited in cyclic process, reduce the cycle performance of material.Meanwhile, nanometer can not solve the problem that SEI film generates caused cycle life decay repeatedly.At present, nanometer tin is dispersed in a kind of conducting base, particularly carbon base body and is considered to a kind of good solution solving above all problems.Such as, Scrosati seminar is by being injected in organogel by the presoma of tin, then this mixture of high temperature pyrolysis has prepared a kind of tin carbon composite, the specific capacity of 500 mAh/g still can be kept after circulation hundreds of week, see: G. Derrien, J. Hassoun, S. Panero, B. Scrosati, Nanostructured Sn-C Composite as an Advanced Anode Material in High-Performance Lithium-Ion Batteries
advance Materials, 2007,19:2336.Recently, the people such as Xu prepare a kind of nanometer tin by aeroge high temperature pyrolytic cracking (HTP) and are dispersed in composite material in carbon ball, the capacity after circulating 130 weeks up to 710 mAh/g, see Y. Xu, Q. Liu, Y. Zhu, Y. Liu, A. Langrock, M. Zachariah, C. Wang
nano Letter,2013
,13:470.The mixture of the synthetic method of present tin carbon composite mainly high temperature pyrolysis carbon source and Xi Yuan.These two kinds of presomas are mixed with to be beneficial in molecule rank and obtain finely dispersed little nano particle.But such mixing ratio is more difficult, the fusing point of adding tin is very low, and it is very difficult that these make to synthesize the extra small nanometer tin particle be dispersed in porous carbon matrix.
Summary of the invention
The object of the invention is to for above-mentioned existing problems, a kind of height ratio capacity is provided, tin carbon composite for lithium secondary battery anode of high cyclical stability and high rate capability and preparation method thereof, by the method for the complex of high temperature pyrolysis tin, the tin nanoparticles of ultra-small grain size is disperseed equably, be embedded in three-dimensional porous carbon support material inner, prepare stanniferous composite material, keep the height ratio capacity characteristic of tin, effectively control the volumetric expansion of overall electrode simultaneously, prevent the reunion of particle, improve its cyclical stability and high rate performance, thus improve energy density and the power density of lithium ion battery negative material.
Technical scheme of the present invention:
A kind of tin carbon composite for lithium secondary battery anode, disperseed equably by the tin nanoparticles of ultra-small grain size, be embedded in three-dimensional porous carbon support material inside and form three-dimensional porous structure, wherein tin nanoparticles is present in tin carbon composite using the tin lithium storage materials with height ratio capacity as stanniferous active material, the particle size range of tin nanoparticles is 5-100 nm, and in composite material, the mass percent of stanniferous active material is 20-70%.
A described preparation method for the tin carbon composite of lithium secondary battery anode, step is as follows:
1) synthesis of (salen) Sn
By stannic chloride and salenH
2part puts into container, adds absolute ethyl alcohol and mixes, then dropwise added by separatory funnel by triethylamine, and gained mixed liquor is 80
oc lower magnetic force stirs 4 hours, naturally cools to 18-25
oc, has a large amount of yellow mercury oxide to generate, and by sediment absolute ethanol washing 2-3 time after filtration, in 100 Pa ~-1 MPa dry 24 hours, obtains (salen) Sn;
2) (salen) Sn is carried out high temperature pyrolysis reaction under protective atmosphere, reaction temperature is 500-1000
oc, heating rate is 2-10
oc/min, the reaction time is 1-10 h, is cooled to 18-25 after reaction terminates
oc, can obtain this tin carbon composite.
Described stannic chloride, salenH
2the mol ratio of part and triethylamine is 1:1:2, absolute ethyl alcohol and salenH
2the amount ratio of part is 20 mL:1 mmol.
The gas of described protective atmosphere is the gaseous mixture of argon gas, nitrogen or argon gas and hydrogen, and in gaseous mixture, the volume ratio of argon gas and hydrogen is 9-19:1.
A described application for the tin carbon composite of lithium secondary battery anode, for the preparation of lithium ion battery, method is as follows:
Tin carbon composite, conductive additive and binding agent are disperseed in organic solvent mixing, on a current collector, then electrode is made in drying in atmosphere, and baking temperature is 323-403 K, and pressure is 100 Pa-1 MPa in coating; With this electrode for work electrode, be to electrode and reference electrode with lithium metal or lithium alloys, two electrodes are separated with barrier film, add electrolyte, in argon gas or dry air, be assembled into lithium secondary battery.
The mass ratio of described tin carbon composite, conductive additive and binding agent is 60-90:10-40:0-20, and the mass ratio of organic solvent and tin carbon composite is 1-20:1.
Described collector is foam copper, nickel foam, copper mesh/sheet, aluminium net/sheet or stainless (steel) wire/sheet; Conductive additive is the mixture of one or more arbitrary proportions in graphite, carbon black, acetylene black and carbon nano-tube; Binding agent is polytetrafluoroethylene, Kynoar, the mixture of one or more arbitrary proportions in polyvinyl alcohol and contracting sodium carboxymethylcellulose pyce; Organic solvent is the mixture of one or more arbitrary proportions in 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), sulfolane, DMF, DMA and caprolactam; Lithium alloys is lithium-aluminium alloy, and wherein the content of lithium is 20-50w%; Barrier film is the film that the mixture of polyethylene, polypropylene, polytetrafluoroethylene and one or more arbitrary proportions cellulosic is formed; Electrolyte is made up of solid lithium salt electrolyte and organic solvent, and solid lithium salt electrolyte concentration is in organic solvent 0.2-1.5 mol/L, and wherein solid lithium salt electrolyte is LiClO
4, LiPF
6, LiBF
4, LiAsF
6, LiCF
3sO
2, LiP (C
6h
4o
2)
3, LiPF
3(C
2f
5)
3, LiB (C
2o
4)
2with LiN (CF
3sO
2)
2the mixture of one or more arbitrary proportions; Solvent is ethylene carbonate, propene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, butylene, carbonic acid first butyl ester and isomer, methyl acetate, methyl propionate, g-butyrolactone, sulfolane, 1,2-dimethoxy-ethane, 1,3-dioxolanes, 4-methyl isophthalic acid, 3-dioxolanes, propiolic acid, oxolane, the mixture of one or more arbitrary proportions in 2-methyltetrahydrofuran and dimethyl sulfoxide (DMSO).
Advantage of the present invention is: this tin carbon composite substantially reduces by nanometer the stress that tin produces in removal lithium embedded process, prevent the efflorescence of particle, three-dimensional porous structure obviously alleviates the bulk effect of active material, effectively prevent the reunion of particle, tin being uniformly distributed in tin carbon composite makes the stress equilibrium produced act on whole electrode, be conducive to the integrality of holding electrode structure, contribute to the capacity and the cyclical stability that improve material, nanometer and porous three-dimensional structure improve the dispersal behavior of lithium in active material jointly, improve the high rate performance of material, the preparation process of this tin carbon composite is easy to control, simple to operate, is convenient to realize industrialization large-scale production, the capacity of this material, cyclical stability and high rate performance are all far superior to graphite negative electrodes system, and the electrical source of power such as electric motor car have potential application prospect.。
Accompanying drawing explanation
Fig. 1 is the XRD figure of this tin carbon compound cathode materials.
Fig. 2 is the TEM photo of this tin carbon compound cathode materials.
Fig. 3 is the prepared constant current first charge-discharge curve of lithium secondary battery under 200 mA/g.
Fig. 4 is that prepared lithium secondary battery cycle charge discharge capacitance under 200 mA/g keeps curve.
Fig. 5 is that the prepared cycle charge discharge capacitance of lithium secondary battery under different multiplying keeps curve.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment:
A kind of tin carbon composite for lithium secondary battery anode, disperseed equably by the tin nanoparticles of ultra-small grain size, be embedded in three-dimensional porous carbon support material inside and form three-dimensional porous structure, wherein tin nanoparticles is present in tin carbon composite using the tin lithium storage materials with height ratio capacity as stanniferous active material, the particle size range of tin nanoparticles is 5-6 nm, and in composite material, the mass percent of stanniferous active material is 56%.
The preparation method of the described tin carbon composite for lithium secondary battery anode, step is as follows:
1) synthesis of (salen) Sn
100 ml absolute ethyl alcohols are joined 0.95 g stannic chloride (5 mmol) and 1.34 g salenH are housed
2in 250 ml three-neck flasks of part (5 mmol), then dropwise added by separatory funnel by 1.4 mL triethylamines (10 mmol), gained mixed liquor is 80
oc lower magnetic force stirs 4 hours, naturally cools to 22
oc, has a large amount of yellow mercury oxide to generate, and by sediment absolute ethanol washing 3 times after filtration, in-1 MPa dry 24 hours, obtains (salen) Sn.
2) preparation of tin carbon composite
(salen) Sn of above-mentioned preparation is proceeded in tube furnace, under argon gas atmosphere 650
oc calcines 2 h, heating rate 5
oc/min, treats that tube furnace temperature is down to 22
oafter C, obtain tin carbon composite.
Fig. 1 is the XRD figure of this tin carbon compound cathode material, shows: all diffraction maximums all belong to and metallic tin (JCPDS card No.4-673) in figure.
Fig. 2 is the TEM photo of this tin carbon compound cathode materials, can see that granular size is that the tin particles of 5 ran disperses uniformly, is embedded in carbon matrix in figure.
Detection shows: during using the tin carbon composite of preparation as lithium ion battery negative, under the current density of 200 mA/g, carry out discharge and recharge, and after circulating 200 weeks, capacity remains on 761 mAh/g; Even if under the high current density of 5000 mA/g, this material still can provide the specific discharge capacity of 500 mAh/g
The tin carbon composite of above-mentioned preparation is for the preparation of lithium secondary battery, and method is as follows:
16 mg tin carbon composites, 2 mg carbon blacks and 2 mg Kynoar are ground to form pulpous state in 80 mL 1-METHYLPYRROLIDONEs, are evenly coated on aluminium foil that diameter is 12 mm, then in-1 MPa air, dryly under 373 K within 10 hours, make electrode slice.In the glove box being full of argon gas, make work electrode with this electrode slice, polyethylene/polypropylene/polyethylene trilamellar membrane makes barrier film, lithium hexafluoro phosphate makes electrolyte at 1 mol/L solution of the volume ratio ethylene carbonate that is 1:1 and dimethyl carbonate mixed solvent, lithium metal is done to be assembled into lithium secondary battery to electrode and reference electrode.
Battery is carried out constant current charge-discharge under 200 mA/g, and discharge voltage range is 0.01-2 V.First charge-discharge curve as shown in Figure 3, shows in figure: discharge capacity and charging capacity are respectively 1175 mAh/g and 980 mAh/g first, and initial coulomb efficiency is 83%.
The cycle charge discharge capacitance of battery under 200 mA/g is kept curve as shown in Figure 4, shows in figure: through circulation in 200 weeks, discharge capacity was 761 mAh/g, coulombic efficiency >99%.
The cycle charge discharge capacitance of this battery under different multiplying keeps curve as shown in Figure 5, and show in figure: the discharge capacity under 5000 mA/g reaches 500 mAh/g, after replying 200 mA/g current densities, capacity gos up to initial level thereupon.Illustrate that this composite material has good cycle performance and superior rate charge-discharge performance.
The foregoing is only certain embodiments of the present invention, be not used for limiting the present invention.In every case the equalization done according to content of the present invention changes and modifies, and is all within protection scope of the present invention.
Claims (3)
1. the preparation method for the tin carbon composite of lithium secondary battery anode, described tin carbon composite is disperseed equably by the tin nanoparticles of ultra-small grain size, it is inner and form three-dimensional porous structure to be embedded in three-dimensional porous carbon support material, wherein tin nanoparticles is present in tin carbon composite using the tin lithium storage materials with height ratio capacity as stanniferous active material, the particle size range of tin nanoparticles is 5-100 nm, in composite material, the mass percent of stanniferous active material is 20-70%, it is characterized in that step is as follows:
1) synthesis of (salen) Sn
By stannic chloride and salenH
2part puts into container, adds absolute ethyl alcohol and mixes, then dropwise added by separatory funnel by triethylamine, and gained mixed liquor is 80
oc lower magnetic force stirs 4 hours, naturally cools to 18-25
oc, has a large amount of yellow mercury oxide to generate, and by sediment absolute ethanol washing 2-3 time after filtration, in 100 Pa ~-1 MPa dry 24 hours, obtains (salen) Sn;
2) (salen) Sn is carried out high temperature pyrolysis reaction under protective atmosphere, reaction temperature is 500-1000
oc, heating rate is 2-10
oc/min, the reaction time is 1-10 h, is cooled to 18-25 after reaction terminates
oc, can obtain this tin carbon composite.
2., according to claim 1 for the preparation method of the tin carbon composite of lithium secondary battery anode, it is characterized in that: described stannic chloride, salenH
2the mol ratio of part and triethylamine is 1:1:2, absolute ethyl alcohol and salenH
2the amount ratio of part is 20 mL:1 mmol.
3. according to claim 1 for the preparation method of the tin carbon composite of lithium secondary battery anode; it is characterized in that: the gas of described protective atmosphere is the gaseous mixture of argon gas, nitrogen or argon gas and hydrogen, in gaseous mixture, the volume ratio of argon gas and hydrogen is 9-19:1.
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| CN105018776B (en) * | 2014-04-30 | 2017-09-29 | 中国科学院金属研究所 | A kind of preparation technology of porous copper foil and its application |
| US9653736B2 (en) * | 2014-08-19 | 2017-05-16 | Powermers Inc. | Method of producing porous metal-carbon materials |
| CN104362319A (en) * | 2014-11-21 | 2015-02-18 | 东莞市迈科科技有限公司 | Preparation method of porous tin-carbon composite negative material |
| CN105810923A (en) * | 2014-12-31 | 2016-07-27 | 中国科学院宁波材料技术与工程研究所 | Preparation method of ultra-small particle size tin and tin-based alloy nano-particle and application thereof |
| CN104638234B (en) * | 2015-01-04 | 2018-11-02 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of negative electrode active material, cathode pole piece and preparation method thereof and lithium ion battery |
| CN105140495A (en) * | 2015-07-15 | 2015-12-09 | 田东 | Method for preparing tin-based anode material by vapor deposition |
| CN105140496A (en) * | 2015-08-07 | 2015-12-09 | 田东 | Preparation method for high-capacity and high-magnification negative electrode material |
| CN109671936B (en) * | 2018-12-19 | 2021-10-29 | 深圳先进技术研究院 | Tin-containing negative electrode material, negative electrode, preparation method of negative electrode material, negative electrode slurry, secondary battery and electric equipment |
| CN110697762B (en) * | 2019-10-15 | 2022-03-29 | 哈尔滨工业大学 | Hollow structure Sn/SnO2Preparation method of @ C lithium ion battery negative electrode material |
| CN112599739B (en) * | 2020-12-14 | 2022-07-12 | 大连海事大学 | Hetero-atom doped mesoporous carbon/tin composite negative electrode material for lithium ion battery and preparation method and application thereof |
| CN112599738B (en) * | 2020-12-14 | 2022-06-03 | 大连海事大学 | Tin-carbon composite material for lithium ion battery cathode and preparation method and application thereof |
| CN112599740B (en) * | 2020-12-14 | 2022-06-03 | 大连海事大学 | Tin disulfide/carbon cathode composite material for lithium ion battery and preparation method and application thereof |
| CN113140708B (en) * | 2021-03-22 | 2022-08-19 | 复旦大学 | Alkaline storage battery based on tin negative electrode |
| CN113880130B (en) * | 2021-12-06 | 2022-04-29 | 中博龙辉装备集团股份有限公司 | Stannous sulfide carbon composite material and preparation method and application thereof |
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| JP5499636B2 (en) * | 2009-10-29 | 2014-05-21 | 住友ベークライト株式会社 | Carbon material for negative electrode of lithium secondary battery, negative electrode of lithium secondary battery and lithium secondary battery |
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| CN101202340A (en) * | 2007-12-07 | 2008-06-18 | 广西师范大学 | Tin carbon nanometer compound material for lithium ion battery and method for making same |
| CN101626075A (en) * | 2009-08-03 | 2010-01-13 | 北京化工大学 | Stannum and carbon composite nano-fiber film negative-electrode material and preparation method thereof |
| CN101700870A (en) * | 2009-11-13 | 2010-05-05 | 无锡中科光远生物材料有限公司 | Preparation method of carbon micron tube encapsulating tin nano material and application thereof |
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