CN102412391A - Preparation method of tin carbon composite nano-material for lithium ion battery cathode - Google Patents
Preparation method of tin carbon composite nano-material for lithium ion battery cathode Download PDFInfo
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- CN102412391A CN102412391A CN2011103212234A CN201110321223A CN102412391A CN 102412391 A CN102412391 A CN 102412391A CN 2011103212234 A CN2011103212234 A CN 2011103212234A CN 201110321223 A CN201110321223 A CN 201110321223A CN 102412391 A CN102412391 A CN 102412391A
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- 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 invention discloses a preparation method of tin carbon composite nano-material for lithium ion battery cathode, comprising the steps as follows: adding a nano-tin precursor and a sugar into the specific organic solvent, dispersing them by ultrasonic wave, transferring them to the hydrothermal reactor, heating up to 160-200 degrees centigrade, keeping the temperature for 30-720 min, after the reaction, centrifuging and separating, and drying them; thermally processing them under the nitrogen atmosphere to obtain a final product. In the method, the nano-precursor is taken as a template and is compounded into the tin carbon composite nano-material via a simple solvent thermal carbonization process. The method simplifies the process step and reduces the cost and can be produced on scale. The solvent thermal process can effectively restrain the oxidation of the metal tin so as to obtain the tin carbon composite nano-material with high purity. The proportion of the tin and the carbon is controllable so that the performance of the lithium ion battery of the tin carbon composite nano-material can be intensively researched.
Description
Technical field
The invention belongs to material science, be specifically related to a kind of preparation method of used as negative electrode of Li-ion battery tin carbon composite nano-material.
Background technology
Owing to have than higher theoretical capacity; Tin base cathode material (metallic tin, tin-based oxide, tinbase sulfide and kamash alloy) is considered to one of substitute of desirable commercial graphite-like material with carbon element, thereby satisfies the demand of high-capacity lithium ion cell of future generation.Than negative materials such as tin-based oxide and sulfide, metallic tin has higher first charge-discharge efficiency, thereby is considered to one of the most promising tin base cathode material.Yet huge change in volume can take place in metallic tin in charge and discharge process, causes electrode material generation efflorescence, and capacity can sharply descend, thereby has limited its application on the commercialization lithium ion battery.
Present increasing work concentrates on and designs the novel combination electrode material based on metallic tin.Wherein, the composite nano materials of tin and carbon can effectively be alleviated the change in volume of metallic tin in cyclic process, thereby receives much attention.At present; In the process of preparation tin and carbon composite nano-material; Often can use the raw material of poisonous organotin and special consersion unit, reaction condition is relatively harsher, and complex steps; Yield poorly, thereby limited a large amount of productions and the application in the commercialization lithium ion battery negative material of tin carbon composite nano-material.
Summary of the invention
The invention provides a kind of preparation method of used as negative electrode of Li-ion battery tin carbon composite nano-material, combine the synthetic tin carbon composite nano-material of follow-up heat treatment process through solvent thermal reaction, the method simple controllable can be mass-produced.
A kind of preparation method of used as negative electrode of Li-ion battery tin carbon composite nano-material may further comprise the steps:
(1) be that 1: 100～1 nanometer tin presoma and carbohydrate join in the organic solvent with mass ratio, ultrasonic dispersion 1～30 minute makes mixed solution; Wherein, described carbohydrate is glucose or sucrose, and described organic solvent is at least a in ethanol, the ethylene glycol;
(2) mixed solution that step (1) is obtained is transferred in the hydrothermal reaction kettle, is warming up to 160～200 ℃, is incubated 30～720 minutes, reduces to room temperature, and centrifugation is also dry;
(3) product that step (2) is obtained is heat-treated in nitrogen atmosphere, and heat treatment temperature is 400～600 ℃, is incubated 30～300 minutes, obtains the tin carbon composite nano-material.
In the optimized technical scheme, described nanometer tin presoma is sijna rice particle, tin nanosphere or tin nanometer rods.
In the optimized technical scheme, in the mixed solution of step (1), the concentration of said carbohydrate is 0.1～100 grams per liter.
Among the present invention, as template, in solvent thermal reaction, by glucose or sucrose carbon source is provided with nanometer tin presoma, the carbon-coating in surperficial uniform deposition one deck controllable thickness of nanometer tin presoma finally forms the tin carbon composite nano-material.
With respect to prior art, the present invention has following beneficial technical effects:
(1) the present invention adopts nanometer tin presoma as template, through the synthetic tin carbon composite nano-material of simple solvent thermal carbonisation, has simplified processing step, has reduced cost, can be mass-produced;
(2) the solvent thermal process of the present invention's employing can effectively suppress the oxidation of metallic tin, thereby can obtain highly purified tin carbon composite nano-material;
(3) ratio of tin and carbon is controlled in the inventive method, helps the further investigation of the performance of follow-up lithium ion battery to the tin carbon composite nano-material.
Description of drawings
The transmission electron microscope photo of the tin carbon composite nano-material that Fig. 1 makes for embodiment 1;
The distribution diagram of element of the tin carbon composite nano-material that the embodiment 1 that Fig. 2 draws for the electron energy loss spectroscopy (EELS) of transmission electron microscope makes;
The high-resolution-ration transmission electric-lens photo of the tin carbon composite nano-material that Fig. 3 makes for embodiment 1;
The X ray diffracting spectrum of the tin carbon composite nano-material that Fig. 4 makes for embodiment 1;
The chemical property figure of the tin carbon composite nano-material that Fig. 5 makes for embodiment 1.
Embodiment
Specify the present invention below in conjunction with embodiment and accompanying drawing, but the present invention is not limited to this.
Embodiment 1:
(1) 50 milligrams of tin nanometer rods and 400 milligrams of glucose are joined in 40 milliliters of ethanolic solutions, and ultrasonic 5 minutes.
(2) mixed solution that step (1) is obtained is transferred in 50 milliliters of hydrothermal reaction kettles, is warming up to 180 ℃, is incubated 180 minutes, reduces to room temperature, and centrifugation is also dry.
(3) product that step (2) is obtained is heat-treated in nitrogen atmosphere, and heat treatment temperature is 500 ℃, is incubated 180 minutes, obtains end product, is the tin carbon composite nano-material.
Fig. 1, Fig. 2, Fig. 3 and Fig. 4 are respectively transmission electron microscope photo, distribution diagram of element, high-resolution-ration transmission electric-lens photo and the X ray diffracting spectrums by the synthetic tin carbon composite nano-material of present embodiment.
The present embodiment synthetic product that Fig. 2 draws for the electron energy loss spectroscopy (EELS) of transmission electron microscope is at the distribution diagram of element of same position; Visiblely among the figure be distributed with tin element (a) and carbon (b) simultaneously, so the present embodiment synthetic product is the tin carbon composite nano-material at same position; In conjunction with Fig. 1, Fig. 3 and Fig. 4, the visible existence that one deck carbon is arranged on the surface of tin uniformly confirms that further synthetic what obtain is the tin carbon composite nano-material to present embodiment.Also visible from Fig. 1, Fig. 3 and Fig. 4; The tin carbon composite nano-material that obtains has been kept the pattern of tin nanometer rods one dimension, and diameter is 40～100 nanometers, and wherein surperficial carbon-coating is even continuously; Thickness is 5～10 nanometers, and X ray diffracting spectrum shows that crystalline phase is the single phase of Sn.From the high-resolution-ration transmission electric-lens photo, can find out tangible tin carbon nucleocapsid structure; Partly have tangible lattice fringe to occur at metallic tin, its interplanar distance is 0.279 nanometer, (101) crystal face of corresponding metallic tin; Surface carbon-coating right and wrong crystalline substance, this is consistent with X ray diffracting spectrum.
Fig. 5 is the chemical property figure by the synthetic tin carbon composite nano-material of present embodiment.From figure, can know that the tin carbon composite nano-material of gained reversible specific capacity first reaches 1104 MAH/grams, through 20 circulations afterwards specific discharge capacity still remain on 800 MAHs/more than the gram.The tin carbon composite nano-material that gained is described demonstrates higher specific capacity and more superior cycle performance, can be expected to be implemented in the commercial applications on the lithium ion battery negative material.
Embodiment 2:
(1) 80 milligrams of sijna rice particles and 80 milligrams of sucrose are joined in 40 milliliters of ethylene glycol solutions, and ultrasonic 1 minute.
(2) mixed solution that step (1) is obtained is transferred in 50 milliliters of hydrothermal reaction kettles, is warming up to 160 ℃, is incubated 720 minutes, reduces to room temperature, and centrifugation is also dry.
(3) product that step (2) is obtained is heat-treated in nitrogen atmosphere, and heat treatment temperature is 400 ℃, is incubated 300 minutes, obtains end product, is the tin carbon composite nano-material.Its result is similar with embodiment 1, and difference is that the tin in the tin carbon composite nano-material is nano particle in this example, rather than nanometer rods.
Embodiment 3:
(1) 8 milligrams of tin nanospheres and 800 milligrams of glucose are joined in 40 milliliters of ethanolic solutions, and ultrasonic 30 minutes.
(2) mixed solution that step (1) is obtained is transferred in 50 milliliters of hydrothermal reaction kettles, is warming up to 200 ℃, is incubated 30 minutes, reduces to room temperature, and centrifugation is also dry.
(3) product that step (2) is obtained is heat-treated in nitrogen atmosphere, and heat treatment temperature is 600 ℃, is incubated 30 minutes, obtains end product, is the tin carbon composite nano-material.Its result is similar with embodiment 1, and difference is that the tin in the tin carbon composite nano-material is nanosphere in this example, rather than nanometer rods.
Embodiment 4:
(1) 80 milligrams of tin nanometer rods and 80 milligrams of sucrose are joined in 40 milliliters of ethylene glycol solutions, and ultrasonic 10 minutes.
(2) mixed solution that step (1) is obtained is transferred in 50 milliliters of hydrothermal reaction kettles, is warming up to 170 ℃, is incubated 300 minutes, reduces to room temperature, and centrifugation is also dry.
(3) product that step (2) is obtained is heat-treated in nitrogen atmosphere, and heat treatment temperature is 450 ℃, is incubated 240 minutes, obtains end product, is the tin carbon composite nano-material.Its result is similar with embodiment 1.
Embodiment 5:
(1) 8 milligrams of tin nanometer rods and 800 milligrams of glucose are joined in 40 milliliters of ethanol and the ethylene glycol mixed solution, and ultrasonic 20 minutes.
(2) mixed solution that step (1) is obtained is transferred in 50 milliliters of hydrothermal reaction kettles, is warming up to 190 ℃, is incubated 120 minutes, reduces to room temperature, and centrifugation is also dry.
(3) product that step (2) is obtained is heat-treated in nitrogen atmosphere, and heat treatment temperature is 550 ℃, is incubated 120 minutes, obtains end product, is the tin carbon composite nano-material.Its result is similar with embodiment 1.
Claims (3)
1. the preparation method of a used as negative electrode of Li-ion battery tin carbon composite nano-material is characterized in that, may further comprise the steps:
(1) be that 1: 100～1 nanometer tin presoma and carbohydrate join in the organic solvent with mass ratio, ultrasonic dispersion 1～30 minute makes mixed solution; Wherein, described carbohydrate is glucose or sucrose, and described organic solvent is at least a in ethanol, the ethylene glycol;
(2) mixed solution that step (1) is obtained is transferred in the hydrothermal reaction kettle, is warming up to 160～200C, is incubated 30～720 minutes, reduces to room temperature, and centrifugation is also dry;
(3) product that step (2) is obtained is heat-treated in nitrogen atmosphere, and heat treatment temperature is 400～600C, is incubated 30～300 minutes, obtains the tin carbon composite nano-material.
2. the preparation method of used as negative electrode of Li-ion battery tin carbon composite nano-material as claimed in claim 1 is characterized in that, described nanometer tin presoma is sijna rice particle, tin nanosphere or tin nanometer rods.
3. the preparation method of used as negative electrode of Li-ion battery tin carbon composite nano-material as claimed in claim 1 is characterized in that, in the mixed solution of step (1), the concentration of said carbohydrate is 0.1～100 grams per liter.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102983315A (en) * | 2012-12-20 | 2013-03-20 | 福州大学 | Method for preparing one-dimensional C/ Sn@C/ C composite nano tubes by using CuO nano wires as template |
| CN103022501A (en) * | 2012-12-05 | 2013-04-03 | 上海锦众信息科技有限公司 | Method for preparing negative-pole tin-carbon composite material for lithium ion battery |
| CN104103808A (en) * | 2014-07-31 | 2014-10-15 | 中国科学院上海硅酸盐研究所 | Flake-like tin-carbon composite material for lithium ion battery and preparation method for flake-like tin-carbon composite material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101771146A (en) * | 2009-01-07 | 2010-07-07 | 清华大学 | Lithium ion battery anode material and preparation method thereof |
| CN102089240A (en) * | 2008-07-15 | 2011-06-08 | 杜伊斯堡-艾森大学 | Intercalation of silicon and/or tin into porous carbon substrates |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102089240A (en) * | 2008-07-15 | 2011-06-08 | 杜伊斯堡-艾森大学 | Intercalation of silicon and/or tin into porous carbon substrates |
| CN101771146A (en) * | 2009-01-07 | 2010-07-07 | 清华大学 | Lithium ion battery anode material and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103022501A (en) * | 2012-12-05 | 2013-04-03 | 上海锦众信息科技有限公司 | Method for preparing negative-pole tin-carbon composite material for lithium ion battery |
| CN102983315A (en) * | 2012-12-20 | 2013-03-20 | 福州大学 | Method for preparing one-dimensional C/ Sn@C/ C composite nano tubes by using CuO nano wires as template |
| CN102983315B (en) * | 2012-12-20 | 2014-07-30 | 福州大学 | Method for preparing one-dimensional C/ Sn@C/ C composite nano tubes by using CuO nano wires as template |
| CN104103808A (en) * | 2014-07-31 | 2014-10-15 | 中国科学院上海硅酸盐研究所 | Flake-like tin-carbon composite material for lithium ion battery and preparation method for flake-like tin-carbon composite material |
| CN104103808B (en) * | 2014-07-31 | 2016-07-27 | 中国科学院上海硅酸盐研究所 | A kind of lithium ion battery lamellar stannum carbon composite and preparation method thereof |
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Application publication date: 20120411 |