CN101944598A - Method for preparing lithium ion battery cathode material - Google Patents
Method for preparing lithium ion battery cathode material Download PDFInfo
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- CN101944598A CN101944598A CN2010102676788A CN201010267678A CN101944598A CN 101944598 A CN101944598 A CN 101944598A CN 2010102676788 A CN2010102676788 A CN 2010102676788A CN 201010267678 A CN201010267678 A CN 201010267678A CN 101944598 A CN101944598 A CN 101944598A
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Abstract
The invention discloses a method for preparing a lithium ion battery cathode material, which comprises the following steps of: (1) dispersing carbon microspheres serving as an intermediate phase into aqueous solution of stannic chloride to obtain mixed solution; (2) making the mixed solution contact with ammonia under vacuum atmosphere to generate white sediment; (3) separating the white sediment and drying the white sediment; and (4) calcining the dried white sediment under the protection of inert gas to obtain the lithium ion battery cathode material. The preparation method overcomes the defects of non-uniform product, long synthesis cycle, high energy consumption and the like in the conventional synthesis method. The obtained SnO2/ C (MBMC) composite material has high reversible capacity and good cycle performance.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ion battery negative material, relate in particular to a kind of SnO
2The preparation method of/C (MBMC) composite material.
Background technology
After nineteen ninety Japan Sony Corporation takes the lead in the lithium rechargeable battery commercialization, but lithium ion battery with its voltage height, energy density is big, self discharge is little, discharge time long fast charging and discharging, have extended cycle life, memory-less effect, advantage such as pollution-free cause the great interest of people and developed rapidly.
At present, business-like lithium ion battery negative material mainly is a material with carbon element, and its advantage is that cost is low, discharge platform is long, and etc. advantage, but the highest theoretical capacity of material with carbon element only is 372mAh/g.Therefore for to satisfy the demand of fields such as portable electronics, electric motor car industry, military equipment and space flight, be necessary to explore novel high-capacity negative material lithium storage materials to high-capacity battery.
Negative material tin ash (the SnO of lithium ion battery
2) theoretical peak capacity be about 1494mAh/g, theoretical reversible capacity can reach 783mAh/g, aspect capacity, has remarkable advantages, but shortcoming is an irreversible capacity height first, account for 50% of theoretical capacity, and the change in volume of material in charge and discharge process is big, cubical expansivity is near 300%, very easily efflorescence in cyclic process finally causes the serious deterioration of cycle performance, has limited its commercialization.In order to solve SnO
2Above-mentioned shortcoming, can reduce the mechanical stress that change in volume causes by adding formation compounds such as some metal oxides, nonmetal oxide, to keep the form of electrode material in charge and discharge process.Wherein a kind of effective way is exactly with nano active SnO
2Dispersion of Particles makes particle still keep each other connectivity when efflorescence in nonmetal basal body.Carbon base body can not only provide conductive channel between tin particles simultaneously, but also can increase lithium storage content.MCMB (MCMB) is as a kind of carbon negative pole material, and its external form is spherical in shape, is the aspect packed structures of high-sequential, and reversible capacity can reach about 300mAh/g, and irreversible capacity is less than 10%, and cycle performance is good.But, influenced the application of MCMB to a certain extent because specific capacity is not high.MCMB is compounded to form SnO as a kind of carbon base body and tin oxide
2No matter/C class composite material is from improving tin oxide first charge-discharge efficiency and cycle performance, or all is a feasible way from the capacity angle that improves negative material.
MCMB MCMB is developed at first, is produced by Osaka, Japan Gas Company and as ion cathode material lithium, its bulk shape presents sphere, is the aspect packed structures of high-sequential.Units such as present China Anshan heat energy institute have also developed this material.MCMB can be made by coal tar (pitch) or petroleum residual oil (pitch), and its graphitization temperature is controlled at more than 2800 ℃ usually, and its reversible capacity can reach 300mAhg
-1About, irreversible capacity is less than 10%, and cycle performance is good.MCMB is one of present long-life small-scale lithium ion cell and the employed main negative material of electrokinetic cell, and is not high but existing questions is a specific capacity, influenced its application to a certain extent.
At present, SnO
2The material with carbon element that adopts in/C the Composite Preparation is graphite, amorphous carbon normally.What synthetic method mainly adopted is mechanical ball milling method, chemical precipitation method, sol-gal process etc., and there are shortcomings such as energy consumption is big, mixing is inhomogeneous, synthesis cycle is long respectively in said method.
Summary of the invention
The invention provides a kind of preparation and synthetic method thereof of lithium ion battery negative material.This material SnO
2/ C (MBMC) is by SnO
2And MCMB is formed, and on the liquid phase synthesizing method basis, improved, adopt the gas phase diffusion method to prepare the more good composite material of performance, its reversible capacity, first charge-discharge efficiency and cycle performance all be improved significantly, and shortened synthesis cycle, reduced energy consumption.
A kind of lithium ion battery negative material SnO
2The preparation method of/C (MBMC) may further comprise the steps:
(1) MCMB is dispersed in the butter of tin aqueous solution obtains mixed liquor;
The described MCMB and the butter of tin aqueous solution be that every 1g MCMB is used the butter of tin aqueous solution 15～50ml with magnitude relation, for example can drop into MCMB 0.3～1.0g in the 15ml butter of tin aqueous solution.
In the described butter of tin aqueous solution, the concentration of butter of tin is 0.075～0.2mol/L;
In order to obtain better dispersion effect, after can in the butter of tin aqueous solution, dropping into MCMB, utilize to stir mode in conjunction with ultrasonic dispersion, for example can first magnetic agitation 1.5h, and then the ultrasonic 0.5h of frequency 99Hz, the mixed liquor that generally obtains is the suspension-turbid liquid state.
(2) mixed liquor contacts with ammonia under vacuum, generates white depositions;
Because step (1) is to operate in reaction vessel, obtain can directly reaction vessel being vacuumized after the mixed liquor and obtain vacuum, in reaction vessel, feed ammonia then, in order to guarantee product property, preferably adopt purity to be not less than 99% ammonia.
The not strict restriction of the consumption of ammonia, because will generate white precipitate by the moment of ammonia, so the consumption of ammonia is very little, even excessive feeding does not have much affect to product yet.
(3) white depositions is separated dry this white depositions;
White depositions can be separated by modes such as centrifugal filtrations, and the temperature during dry white depositions is 60～100 ℃, and be 10～48h drying time, preferably at 80 ℃ of dry 10h.
(4) dried white depositions is calcined under inert gas shielding, obtain described lithium ion battery negative material.
Because white depositions has the part caking phenomenon when dry, therefore can utilize agate mortar earlier dried white depositions fully to be ground in the step (3), calcine then.
Calcining is to adopt general device, but needs inert gas shielding, and inert gas can be an argon gas etc.
Heating rate during calcining is 8～12 ℃/min, until being warming up to 500～800 ℃, calcines 2～15h, and the heating rate during as preferred calcining is 10 ℃/min, until being warming up to 650 ℃, at 650 ℃ of calcining 3h.
Technical scheme of the present invention has overcome shortcomings such as existing synthetic method products obtained therefrom is inhomogeneous, synthesis cycle is long, energy consumption is big.The prepared SnO that obtains
2/ C (MBMC) composite material possesses higher reversible capacity and better cycle performance.
Description of drawings
Fig. 1 is SnO
2, MBMC, SnO
2/ C (a) ten all circulating and reversible capacity comparison diagrams;
Fig. 2 is SnO
2/ C (MBMC) composite sample a, sample b, sample c 13 all circulating and reversible capacity comparison diagrams;
Fig. 3 is SnO
2/ C (MBMC) composite sample d, sample e, sample f 13 all circulating and reversible capacity comparison diagrams;
Fig. 4 is sample a 40 all cycle charge discharge capacitances and efficiency charts;
Fig. 5 is sample d 40 all cycle charge discharge capacitances and efficiency charts.
Embodiment
Embodiment 1
Getting the 15ml molar concentration is the commercial MCMB of butter of tin aqueous solution adding 1.0g of 0.075mol/L, places 50ml small beaker magnetic agitation 1.5h, and the ultrasonic 0.5h of frequency 99Hz fully scatter MCMB.The suspension-turbid liquid dislocation is had in the round-bottomed flask of two-way cock, vacuumize in the round-bottomed flask.Use purity is 99% ammonia, and ammonia is filled in leather bag, clamps with the Huffman folder.With leather bag with open cock and Huffman folder after the round-bottomed flask two-way cock links to each other, moment generates white precipitate in the round-bottomed flask.The precipitation that obtains after centrifugation, 80 ℃, 10h oven dry.Agate mortar fully grinds the back with tubular type atmosphere furnace argon gas atmosphere (argon gas flow velocity 80ml/min), 10 ℃/min of heating rate, 650 ℃ of calcining 3h, obtains black powder.
8: 1: 1 synthetic material of mass ratio (black powder that obtains), acetylene black and Kynoar (PVDF) are dissolved in the solvent N-methyl pyrrolidone.Ultrasonic, stirring hockets slurry is mixed.Slurry is evenly coated on the Copper Foil, and it is 1cm that 80 ℃ of oven dry back punchings in following 3 hours become big small size
2Work electrode.Suppress cutting out good work electrode, thickness is about 75um before the compacting, and compacting back thickness is about 30um.Down oven dry 7-8 hour is standby at 100 ℃ again after the compacting.Test battery adopts 2032 type button cells, is to electrode with metallic lithium foil, and the EC-DMC of the LiPF6 of 1mol/L (volume ratio is 1: 1) solution is electrolyte, is assembled in glove box.Carry out the constant current charge-discharge test with 0.1C.Capacity remains on 482.4mAh/g after the circulation of ten weeks, and capability retention is 90%.After the circulation of 40 weeks, capacity remains on 371.6mAh/g, and capability retention is 88.2%.
Getting the 15ml molar concentration is the commercial MCMB of butter of tin aqueous solution adding 1.0g of 0.125mol/L.Carry out following operation according to embodiment 1 step, prepare the black powder composite material.The test of assembling button cell 0.1C constant current charge-discharge.After the circulation of 40 weeks, capacity remains on 350.5mAh/g, and capability retention is 79.4%.
Embodiment 3
Getting the 15ml molar concentration is the commercial MCMB of butter of tin aqueous solution adding 1.0g of 0.2mol/L.According to the operation of embodiment 1 step, the test of preparation button cell 0.1C constant current charge-discharge.After the circulation of 40 weeks, capacity remains on 336.9mAh/g, and capability retention is 70.3%.
Getting the 15ml molar concentration is the commercial MCMB of butter of tin aqueous solution adding 0.3g of 0.075mol/L, according to the operation of embodiment 1 step, and the test of preparation button cell 0.1C constant current charge-discharge.After the circulation of 40 weeks, capacity remains on 422.2mAh/g, and capability retention is 81.1%.
Embodiment 5
Getting the 15ml molar concentration is the commercial MCMB of butter of tin aqueous solution adding 0.3g of 0.075mol/L.According to the operation of embodiment 1 step, the test of preparation button cell 0.1C constant current charge-discharge.After the circulation of 40 weeks, capacity remains on 313.2mAh/g, and capability retention is 51.2%.
Getting the 15ml molar concentration is the commercial MCMB of butter of tin aqueous solution adding 0.3g of 0.075mol/L.According to the operation of embodiment 1 step, the test of preparation button cell 0.1C constant current charge-discharge.After the circulation of 40 weeks, capacity remains on 229.3mAh/g, and capability retention is 36.0%.
Comparative Examples 1
With the synthetic SnO of liquid phase method
2Be negative material, press 8: 1: 1 negative material of mass ratio, acetylene black and Kynoar (PVDF), carry out the constant current charge-discharge test with 0.1C with embodiment 1 assembling button cell.After the circulation of ten weeks, capacity attenuation is 270.2mAh/g, and capability retention is 30%.
Comparative Examples 2
With MCMB (MCMB) is negative material.Press 8: 1: 1 negative material of mass ratio, acetylene black and Kynoar (PVDF) with embodiment 1 assembling button cell, carry out the constant current charge-discharge test with 0.1C.After the circulation of ten weeks, capacity remains on 314.0mAh/g, and capability retention is 97.3%.
Performance test
Abscissa among Fig. 1 to Fig. 5 is the circulating cycle issue, and ordinate is a specific discharge capacity.Lithium ion battery negative material SnO2/C composite sample a, b, c, d, e, f (a, b, c, d, six samples of e, f are respectively from embodiment 1～6) have been prepared according to preparation method of the present invention.
Fig. 1 is the SnO of preparation
2/ C composite sample a, SnO
2, MBMC preceding ten loop cycle reversible capacities relatively.As can be seen from the figure compare SnO with MCMB, SnO2
2The capacity of/C obviously improves, and circulation improves;
Fig. 2 is the identical SnO of MCMB doping
2The reversible capacity in/C sample a, preceding 13 weeks of b, c relatively.As can be seen from the figure three's loop attenuation trend unanimity, the reversible capacity of sample a, b remains on about 420mAh/g substantially, and sample c exceeds about 50mAh/g than the above two, about 470mAh/g;
Fig. 3 is the identical SnO of MCMB doping
2The reversible capacity in/C sample d, preceding 13 weeks of e, f relatively.As can be seen from the figure three's loop attenuation trend is also consistent, and the reversible capacity of sample d remains on about 500mAh/g substantially, the reversible capacity of sample e, f apparently higher than the former about 580mAh/g.The advantage of sample a, d highlights after 40 loop cycle.
Fig. 4 is 40 loop cycle reversible capacities and the efficiency for charge-discharge figure of sample a.This material 40 all circulating and reversible capacity held stationaries as can be seen among the figure, the circulation of 40 weeks remains on 370mAh/g.From efficiency for charge-discharge figure find out this material first efficient reached 76%, since second round coulomb efficient reach more than 90% and progressively and increase, arrive the 8th all circulation times and reach 99.4%, and next remaining on about this numerical value in more than 30 circulation, the highlyest can reach 99.8%, cycle performance is superior.
Fig. 5 is 40 loop cycle reversible capacities and the efficiency for charge-discharge figure of sample d.As can be seen from the figure the efficient of enclosed pasture first of this material is more lower slightly than sample a, enclosed pasture efficient progressively raises in the preceding ten week circulations, has reached 99.1% during the tenth week, though after circulation in enclosed pasture efficient fluctuate bigger than sample a, but still not being lower than 98%, cycle performance is good.The considerable 40 weeks circulation of its capacity has still reached 422.2mAh/g, exceeds 120mAh/g than mixing with MCMB, has reached 53.9% of the theoretical reversible capacity of tin oxide simultaneously.
Claims (9)
1. the preparation method of a lithium ion battery negative material is characterized in that, may further comprise the steps:
(1) MCMB is dispersed in the butter of tin aqueous solution obtains mixed liquor;
(2) mixed liquor contacts with ammonia under vacuum, generates white depositions;
(3) white depositions is separated dry this white depositions;
(4) dried white depositions is calcined under inert gas shielding, obtain described lithium ion battery negative material.
2. the preparation method of lithium ion battery negative material as claimed in claim 1 is characterized in that, every 1g MCMB is used the butter of tin aqueous solution 15～50ml in the step (1).
3. the preparation method of lithium ion battery negative material as claimed in claim 2 is characterized in that, in the described butter of tin aqueous solution of step (1), the concentration of butter of tin is 0.075～0.2mol/L.
4. the preparation method of lithium ion battery negative material as claimed in claim 3 is characterized in that, step (1) drops into MCMB in the butter of tin aqueous solution, and first magnetic agitation is carried out the mixed liquor that ultrasonic dispersion obtains then.
5. the preparation method of lithium ion battery negative material as claimed in claim 1 is characterized in that, the purity of ammonia is not less than 99% in the step (2).
6. the preparation method of lithium ion battery negative material as claimed in claim 1 is characterized in that, the temperature in the step (3) during dry white depositions is 60～100 ℃, and be 10～48h drying time.
7. the preparation method of lithium ion battery negative material as claimed in claim 1 is characterized in that, earlier dried white depositions is ground in the step (4), calcines then.
8. the preparation method of lithium ion battery negative material as claimed in claim 7 is characterized in that, the heating rate when calcining in the step (4) is 10 ℃/min, until being warming up to 500～800 ℃.
9. the preparation method of lithium ion battery negative material as claimed in claim 8 is characterized in that, calcining 2～15h in the step (4).
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| CN201010267678A CN101944598B (en) | 2010-08-31 | 2010-08-31 | Method for preparing lithium ion battery cathode material |
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| CN201010267678A CN101944598B (en) | 2010-08-31 | 2010-08-31 | Method for preparing lithium ion battery cathode material |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103400698A (en) * | 2013-07-29 | 2013-11-20 | 奇瑞汽车股份有限公司 | Method of pulping through powder, photo-anode of dye-sensitized solar cell and dye-sensitized solar cell |
| CN103606696A (en) * | 2013-11-15 | 2014-02-26 | 江苏天鹏电源有限公司 | High-capacity and low-energy-consumption lithium ion battery |
| CN108470882A (en) * | 2018-03-30 | 2018-08-31 | 江汉大学 | Tin oxide is modified carbon cloth base lithium and sodium metal negative electrode and preparation method thereof |
| CN112366319A (en) * | 2019-12-31 | 2021-02-12 | 广东天劲新能源科技股份有限公司 | Composite nano SnO2Preparation method of negative electrode material and mesocarbon microbeads |
| CN118164524A (en) * | 2024-03-21 | 2024-06-11 | 商丘师范学院 | Amorphous tin oxide/mesophase carbon microsphere composite material and preparation method and application thereof |
-
2010
- 2010-08-31 CN CN201010267678A patent/CN101944598B/en active Active
Non-Patent Citations (4)
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| 《Electrochimica Acta》 20040730 G.X.Wang Electrochemical characteristics of tin-coated MCMB graphite as anode in Lithium-ion cells 第517-522页 1-9 第50卷, * |
| 《Journal of power sources》 20070810 Shubin Yang,et al. Nanosized tin and tin oxides loaded expanded mesocarbon microbeads as negative electrode material for lithium-ion batteries 第487-494页 1-9 第173卷, * |
| 《功能材料》 20061231 Qi Zhi，Wu Feng A study on SnO2-MCMB composite as electrode material for Li-ion cell 第334-337页 1-9 第37卷, 第2期 * |
| 《现代化工》 20041130 齐智，吴锋 用于锂离子电池负极SnO2-MCMB复合材料的研究 第40-42页，第46页 1-9 第24卷, 第11期 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103400698A (en) * | 2013-07-29 | 2013-11-20 | 奇瑞汽车股份有限公司 | Method of pulping through powder, photo-anode of dye-sensitized solar cell and dye-sensitized solar cell |
| CN103606696A (en) * | 2013-11-15 | 2014-02-26 | 江苏天鹏电源有限公司 | High-capacity and low-energy-consumption lithium ion battery |
| CN108470882A (en) * | 2018-03-30 | 2018-08-31 | 江汉大学 | Tin oxide is modified carbon cloth base lithium and sodium metal negative electrode and preparation method thereof |
| CN112366319A (en) * | 2019-12-31 | 2021-02-12 | 广东天劲新能源科技股份有限公司 | Composite nano SnO2Preparation method of negative electrode material and mesocarbon microbeads |
| CN112366319B (en) * | 2019-12-31 | 2022-06-14 | 广东天劲新能源科技股份有限公司 | Composite nano SnO2Preparation method of negative electrode material and mesocarbon microbeads |
| CN118164524A (en) * | 2024-03-21 | 2024-06-11 | 商丘师范学院 | Amorphous tin oxide/mesophase carbon microsphere composite material and preparation method and application thereof |
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Address after: 300384 Tianjin Huayuan Industrial Park No. 5 Yuan Lu GUI Patentee after: Tianjin Bamo Technology Co.,Ltd. Address before: 300384 Tianjin Huayuan Industrial Park No. 5 Yuan Lu GUI Patentee before: TIANJIN B & M SCIENCE AND TECHNOLOGY JOINT-STOCK Co.,Ltd. |