CN103346304A - 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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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 use, particularly a kind of tin carbon composite for lithium secondary battery anode and preparation method thereof.
Background technology
Along with the eager demand of electrical source of power such as electric automobile to electrical power storage, energy and the power density of lithium ion battery Yin Qigao are more and more barred up.The negative material of present business-like lithium ion battery is graphite, its low theoretical capacity (372 mAh/g) can not satisfy people for the pursuit of high-energy and high power density, this will ask for help develop have high power capacity, the novel negative material of high cyclical stability and high rate capability.Metal simple-substance tin has high theoretical specific capacity (992 mAh/g), low embedding lithium current potential, is considered to lithium ion battery of future generation one of the most promising negative material.But tin can be followed big change in volume in charge and discharge process, causes the efflorescence of particle and the disengaging of active material and collector, causes the rapid decline of capacity.On the other hand, because tin repeatedly change in volume in cyclic process, can make reaction on electrode material and the electrolyte interface generate solid electrolyte circle Mian Mo (SEI film) breaking and generates repeatedly, constantly consume electrolyte so that the final cycle life that influences battery.These have all seriously limited the application of tin negative pole material.
The size of tin negative pole material is reduced to nanoscale can be reduced to take off/stress that produces in the embedding lithium process, prevent breaking and efflorescence of material, referring to: 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, reduces the cycle performance of material.Simultaneously, nanometer can not solve the problem that the SEI film generates caused cycle life decay repeatedly.At present, nanometer tin is dispersed in is considered to a kind of good solution that solves above all problems in a kind of conducting base, particularly carbon base body.For example, Scrosati seminar is injected in the organogel by the presoma with tin, this mixture of high temperature pyrolysis has prepared a kind of tin carbon composite then, the specific capacity that after circulation hundreds of week, still can keep 500 mAh/g, referring to: 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, people such as Xu prepare a kind of nanometer tin by the aeroge high temperature pyrolytic cracking (HTP) and are dispersed in composite material in the carbon ball, and the capacity after 130 weeks of circulating is up to 710 mAh/g, referring to: Y. Xu, Q. Liu, Y. Zhu, Y. Liu, A. Langrock, M. Zachariah, C. Wang
Nano Letter,2013
,13:470.The synthetic method of tin carbon composite mainly is the mixture of high temperature pyrolysis carbon source and Xi Yuan now.These two kinds of presomas are mixed with to be beneficial in the molecule rank obtain finely dispersed little nano particle.But such mixing ratio is difficulty, and the fusing point of adding tin is very low, and these make that the synthetic extra small nanometer tin particles that is dispersed in the porous carbon matrix is very difficult.
Summary of the invention
The objective of the invention is at above-mentioned existing problems, a kind of height ratio capacity is provided, tin carbon composite that is used for lithium secondary battery anode of high cyclical stability and high rate capability and preparation method thereof, the method of the complex by high temperature pyrolysis tin is disperseed the sijna rice uniform particles ground of ultra-small grain size, be embedded in three-dimensional porous carbon support material inside, the composite material of preparation stanniferous, the height ratio capacity characteristic that keeps tin, the effectively volumetric expansion of control overall electrode simultaneously, prevent the reunion of particle, improve its cyclical stability and high rate performance, thereby 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, sijna rice uniform particles ground by ultra-small grain size disperses, is embedded in three-dimensional porous carbon support material inside and forms three-dimensional porous structure, wherein sijna rice particle is present in the tin carbon composite as the stanniferous active material with the tin lithium storage materials with height ratio capacity, sijna rice particle grain size scope is 5-100 nm, and the mass percent of stanniferous active material is 20-70% in the composite material.
A kind of preparation method of described tin carbon composite for lithium secondary battery anode, step is as follows:
1) (salen) Sn synthetic
With stannic chloride and salenH
2Part is put into container, adds absolute ethyl alcohol and mixes, and then triethylamine is dropwise added by separatory funnel, and the gained mixed liquor is 80
oThe C lower magnetic force stirred 4 hours, naturally cooled to 18-25
oC has a large amount of yellow mercury oxides to generate, and with sediment absolute ethanol washing 2-3 time, drying is 24 hours in 100 Pa ~-1 MPa, obtains (salen) Sn after the filtration;
2) (salen) Sn is carried out the high temperature pyrolysis reaction under protective atmosphere, reaction temperature is 500-1000
oC, heating rate are 2-10
oC/min, the reaction time is 1-10 h, reaction is cooled to 18-25 after finishing
oC can make 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 the volume ratio of argon gas and hydrogen is 9-19:1 in the gaseous mixture.
A kind of application of described tin carbon composite for 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 to mix in organic solvent, be coated on the collector, make electrode at air drying then, baking temperature is 323-403 K, and pressure is 100 Pa-1 MPa; Be work electrode with this electrode, with lithium metal or contain lithium alloy for to electrode and reference electrode, two electrodes are separated with barrier film, add electrolyte, are assembled into lithium secondary battery in argon gas or dry air.
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 the carbon nano-tube; Binding agent is polytetrafluoroethylene, Kynoar, the mixture of one or more arbitrary proportions in polyvinyl alcohol and the contracting sodium carboxymethylcellulose pyce; Organic solvent is N-methyl pyrrolidone, dimethyl sulfoxide (DMSO), sulfolane, N, dinethylformamide, N, the mixture of one or more arbitrary proportions in N-dimethylacetylamide and the caprolactam; Containing lithium alloy 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 cellulosic one or more arbitrary proportions constitutes; Electrolyte is made up of solid lithium salts electrolyte and organic solvent, and the concentration of solid lithium salts electrolyte in organic solvent is 0.2-1.5 mol/L, and wherein solid lithium salts 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)
2And 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 thereof, methyl acetate, methyl propionate, g-butyrolactone, sulfolane, 1,2-dimethoxy-ethane, 1,3-dioxolanes, 4-methyl isophthalic acid, the 3-dioxolanes, propiolic acid, oxolane, the mixture of one or more arbitrary proportions in 2-methyltetrahydrofuran and the dimethyl sulfoxide (DMSO).
Advantage of the present invention is: this tin carbon composite has obviously reduced the stress that tin produces by nanometer in the removal lithium embedded process, prevented the efflorescence of particle, three-dimensional porous structure has obviously alleviated the bulk effect of active material, effectively prevented the reunion of particle, the even distribution of tin in the tin carbon composite makes the stress stepless action that produces on entire electrode, be conducive to keep the integrality of electrode structure, capacity and the cyclical stability of material have been helped to improve, nanometer and porous three-dimensional structure have been improved the dispersal behavior of lithium in active material jointly, have improved the high rate performance of material; The preparation process of this tin carbon composite is easy to control, and is simple to operate, is convenient to realize large-scale industrialization production; The capacity of this material, cyclical stability and high rate performance all are far superior to graphite-like negative pole system, have potential application prospect in electrical source of power such as electric motor cars.。
Description of drawings
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, sijna rice uniform particles ground by ultra-small grain size disperses, is embedded in three-dimensional porous carbon support material inside and forms three-dimensional porous structure, wherein sijna rice particle is present in the tin carbon composite as the stanniferous active material with the tin lithium storage materials with height ratio capacity, sijna rice particle grain size scope is 5-6 nm, and the mass percent of stanniferous active material is 56% in the composite material.
The preparation method of described tin carbon composite for lithium secondary battery anode, step is as follows:
1) (salen) Sn synthetic
100 ml absolute ethyl alcohols are joined 0.95 g stannic chloride (5 mmol) and 1.34 g salenH are housed
2In the 250 ml three-neck flasks of part (5 mmol), then 1.4 mL triethylamines (10 mmol) are dropwise added by separatory funnel, the gained mixed liquor is 80
oThe C lower magnetic force stirred 4 hours, naturally cooled to 22
oC has a large amount of yellow mercury oxides to generate, and with sediment absolute ethanol washing 3 times, drying is 24 hours in-1 MPa, obtains (salen) Sn after the filtration.
2) preparation of tin carbon composite
(salen) Sn of above-mentioned preparation is changed in the tube furnace, under argon gas atmosphere 650
oC calcines 2 h, heating rate 5
oC/min treats that the tube furnace temperature is down to 22
oBehind the C, namely get the tin carbon composite.
Fig. 1 is the XRD figure of this tin carbon compound cathode material, and show among the figure: all diffraction maximums all belong to and metallic tin (JCPDS card No.4-673).
Fig. 2 is the TEM photo of this tin carbon compound cathode materials, can see among the figure that granular size is that tin particles about 5 nanometers disperses uniformly, is embedded in the carbon matrix.
Detection shows: the tin carbon composite of preparation during as lithium ion battery negative, is discharged and recharged under the current density of 200 mA/g, 200 week of circulation the back capacity remain on 761 mAh/g; Even 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 N-methyl pyrrolidones, evenly are coated on the aluminium foil that diameter is 12 mm, then in-1 MPa air, made electrode slice under 373 K in dry 10 hours.Making work electrode, polyethylene/polypropylene/polyethylene trilamellar membrane with this electrode slice in being full of the glove box of argon gas, to make barrier film, lithium hexafluoro phosphate be that the ethylene carbonate of 1:1 and 1 mol of dimethyl carbonate mixed solvent/L solution are made electrolyte, lithium metal is done electrode and reference electrode are assembled into lithium secondary battery in volume ratio.
Battery is carried out constant current charge-discharge under 200 mA/g, discharge voltage range is 0.01-2 V.The first charge-discharge curve shows among the figure as shown in Figure 3: discharge capacity and charging capacity are respectively 1175 mAh/g and 980 mAh/g first, and coulombic efficiency is 83% first.
The cycle charge discharge capacitance of battery under 200 mA/g kept curve as shown in Figure 4, show among the figure: through the circulation of 200 weeks, discharge capacity is 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 among the figure: the discharge capacity under 5000 mA/g reaches 500 mAh/g, reply 200 mA/g current densities after capacity go up to initial level thereupon.Illustrate that this composite material has excellent cycle performance and superior rate charge-discharge performance.
The above only is part example of the present invention, is not to limit the present invention.In every case the equalization of doing according to content of the present invention changes and modifies, and all is within protection scope of the present invention.
Claims (7)
1. tin carbon composite that is used for lithium secondary battery anode, it is characterized in that: the sijna rice uniform particles ground by ultra-small grain size disperses, is embedded in three-dimensional porous carbon support material inside and forms three-dimensional porous structure, wherein sijna rice particle is present in the tin carbon composite as the stanniferous active material with the tin lithium storage materials with height ratio capacity, sijna rice particle grain size scope is 5-100 nm, and the mass percent of stanniferous active material is 20-70% in the composite material.
2. preparation method who is used for the tin carbon composite of lithium secondary battery anode according to claim 1 is characterized in that step is as follows:
1) (salen) Sn synthetic
With stannic chloride and salenH
2Part is put into container, adds absolute ethyl alcohol and mixes, and then triethylamine is dropwise added by separatory funnel, and the gained mixed liquor is 80
oThe C lower magnetic force stirred 4 hours, naturally cooled to 18-25
oC has a large amount of yellow mercury oxides to generate, and with sediment absolute ethanol washing 2-3 time, drying is 24 hours in 100 Pa ~-1 MPa, obtains (salen) Sn after the filtration;
2) (salen) Sn is carried out the high temperature pyrolysis reaction under protective atmosphere, reaction temperature is 500-1000
oC, heating rate are 2-10
oC/min, the reaction time is 1-10 h, reaction is cooled to 18-25 after finishing
oC can make this tin carbon composite.
3. according to the preparation method of the described tin carbon composite for lithium secondary battery anode of claim 2, 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.
4. according to the preparation method of the described tin carbon composite for lithium secondary battery anode of claim 2; it is characterized in that: the gas of described protective atmosphere is the gaseous mixture of argon gas, nitrogen or argon gas and hydrogen, and the volume ratio of argon gas and hydrogen is 9-19:1 in the gaseous mixture.
5. application that is used for the tin carbon composite of lithium secondary battery anode according to claim 1 is characterized in that for the preparation of lithium ion battery, method is as follows:
Tin carbon composite, conductive additive and binding agent are disperseed to mix in organic solvent, be coated on the collector, make electrode at air drying then, baking temperature is 323-403 K, and pressure is 100 Pa-1 MPa; Be work electrode with this electrode, with lithium metal or contain lithium alloy for to electrode and reference electrode, two electrodes are separated with barrier film, add electrolyte, are assembled into lithium secondary battery in argon gas or dry air.
6. according to the application of the described tin carbon composite for lithium secondary battery anode of claim 5, it is characterized in that: 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.
7. according to the application of the described tin carbon composite for lithium secondary battery anode of claim 5, it is characterized in that: 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 the carbon nano-tube; Binding agent is polytetrafluoroethylene, Kynoar, the mixture of one or more arbitrary proportions in polyvinyl alcohol and the contracting sodium carboxymethylcellulose pyce; Organic solvent is N-methyl pyrrolidone, dimethyl sulfoxide (DMSO), sulfolane, N, dinethylformamide, N, the mixture of one or more arbitrary proportions in N-dimethylacetylamide and the caprolactam; Containing lithium alloy 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 cellulosic one or more arbitrary proportions constitutes; Electrolyte is made up of solid lithium salts electrolyte and organic solvent, and the concentration of solid lithium salts electrolyte in organic solvent is 0.2-1.5 mol/L, and wherein solid lithium salts 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)
2And 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 thereof, methyl acetate, methyl propionate, g-butyrolactone, sulfolane, 1,2-dimethoxy-ethane, 1,3-dioxolanes, 4-methyl isophthalic acid, the 3-dioxolanes, propiolic acid, oxolane, the mixture of one or more arbitrary proportions in 2-methyltetrahydrofuran and the dimethyl sulfoxide (DMSO).
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| CN109671936A (en) * | 2018-12-19 | 2019-04-23 | 深圳先进技术研究院 | Containing tin negative pole material, cathode and preparation method thereof and negative electrode slurry, secondary cell and electrical equipment |
| 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 |
| CN110697762A (en) * | 2019-10-15 | 2020-01-17 | 哈尔滨工业大学 | Hollow structure Sn/SnO2Preparation method of @ C lithium ion battery negative electrode material |
| 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 |
| CN112599739A (en) * | 2020-12-14 | 2021-04-02 | 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 |
| CN112599740A (en) * | 2020-12-14 | 2021-04-02 | 大连海事大学 | Tin disulfide/carbon cathode composite material for lithium ion battery and preparation method and application thereof |
| CN112599738A (en) * | 2020-12-14 | 2021-04-02 | 大连海事大学 | Tin-carbon composite material for lithium ion battery cathode 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 |
| CN113140708A (en) * | 2021-03-22 | 2021-07-20 | 复旦大学 | Alkaline storage battery based on tin cathode |
| CN113880130A (en) * | 2021-12-06 | 2022-01-04 | 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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