CN103000881A - Positive material, namely tin-doped lithium cobalt oxide, for lithium ion cell, and preparation method of positive material - Google Patents
Positive material, namely tin-doped lithium cobalt oxide, for lithium ion cell, and preparation method of positive material Download PDFInfo
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- CN103000881A CN103000881A CN2012105489833A CN201210548983A CN103000881A CN 103000881 A CN103000881 A CN 103000881A CN 2012105489833 A CN2012105489833 A CN 2012105489833A CN 201210548983 A CN201210548983 A CN 201210548983A CN 103000881 A CN103000881 A CN 103000881A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to a positive material, namely tin-doped lithium cobalt oxide, for a lithium ion cell, and a preparation method of the positive material. The preparation method comprises the following steps of: mixing a cobalt compound and a lithium compound in proportion, calcining the cobalt compound and the lithium compound at a high temperature for first synthesis to obtain lithium cobalt oxide, and grinding and smashing the lithium cobalt oxide; and mixing a tin component and the ground and smashed lithium cobalt oxide as raw materials in proportion, calcining the raw materials which are mixed uniformly for second synthesis to obtain tin-doped lithium cobalt oxide, and grinding and smashing the tin-doped lithium cobalt oxide, thus obtaining the finished product. The positive material is uniform in particle distribution and intact in crystallinity; the circulating performance of the positive material is excellent, and the primary specific discharge capacity of the positive material in charging and discharging at 0.2C rate is high; and the positive material is good in safety performance and can pass testes of stabbing by a needle, extrusion, impact, internal or external short circuit, overcharging, thermal abuse and the like.
Description
Technical field
The present invention relates to the modified technique of anode material of lithium battery, especially tin dope type cobalt acid lithium and preparation method thereof.
Background technology
Since Sony Corporation in 1991 put lithium ion battery on market, the portable type electronic products such as mobile phone, notebook computer and digital product were day by day strong to the demand of the battery of high performance-price ratio.LiCoO
2As anode material for lithium-ion batteries, its function admirable, but because the positive electrode great majority of at present commercial Li-ion battery employing are pure cobalt acid lithium, the cobalt resource shortage, and the cobalt that mixes acid lithium surface structure is irregular, unstable, make cycle performance of lithium ion battery poor, capacity attenuation is very fast, being prone to surface structure in cyclic process destroys, cause that the internal resistance of cell raises, acutely discharging and recharging under environment or the short-circuit conditions, the heat of accumulating raises battery temperature, positive electrode can discharge oxygen with the electrolyte reaction and cause pressure to increase, and causes battery explosion, thereby has affected cycle performance and the safety in utilization of lithium ion battery.So good cycle, the research and development of the lithium ion battery that security performance is high are paid attention to day by day, and positive electrode has caused concern in the industry as the critical material of lithium ion battery, and therefore, people are devoted to the research and development of anode material for lithium-ion batteries.
Summary of the invention
For the deficiency that prior art exists, the invention provides that a kind of cobalt content is low, specific capacity is high, the anode material for lithium-ion batteries tin dope type cobalt of good, the surperficial mechanism of fail safe rule acid lithium and preparation method thereof.
For reaching above purpose, the present invention solves the technical method that its technical problem adopts and is: cobalt compound and lithium compound are mixed in proportion, and it is synthetic that first time carried out at high temperature calcining, and the cobalt acid lithium that obtains is ground, and obtains A and expect; Expect to mix in proportion as raw material take tin compound and A, mix rear calcining, carry out the second time and synthesize, and the cobalt acid lithium that obtains is ground, obtain mixing the cobalt acid lithium finished product of tin, its chemical formula LiSn
1-xCo
xO
2
After adopting above technical scheme, the invention has the beneficial effects as follows: cobalt acid lithium material even particle distribution among the present invention has intact degree of crystallinity; Cycle performance is good, the 0.2C rate charge-discharge to put first a specific capacity high; Security performance is good, can be by acupuncture, extruding, bump, interior or external short circuit, overcharge, the test such as heat abuse.
Description of drawings
The SEM collection of illustrative plates of positive electrode under electron microscope of Fig. 1 embodiment 1 preparation.
The phase XRD collection of illustrative plates of the positive electrode of Fig. 2 embodiment 1 preparation.
The positive electrode first discharge specific capacity figure of Fig. 3 embodiment 1 preparation.
Embodiment
A kind of anode material for lithium-ion batteries tin dope of the present invention type cobalt acid lithium and preparation method thereof mixes cobalt compound and lithium compound in proportion, and it is synthetic that the first time is carried out at high temperature calcining, and the cobalt acid lithium that obtains is ground, and obtains the A material; Take tin compound and A material as raw material mixes in proportion, mixing rear calcining, to carry out second time synthetic, and the sour lithium of cobalt of tin dope is ground, and obtains finished product.Described ratio is that the molar ratio of lithium compound and cobalt compound is Li/Co=(1.00～1.06)/1.00, and tin compound and cobalt compound molar ratio are for being Sn/Co=(0.03～0.05)/1.00; Described incorporation time is 2～3 hours.Described calcining, its condition are 800～980 ℃ of temperature, 9～11 hours time, pass into air in the calcination process, and flow is (2～3) m
3/ h.
The present invention adopts metallic element Sn at the surface doping of cobalt acid lithium particle, in the situation that less its of cobalt acid lithium particle has higher specific capacity and lower cobalt content.The positive electrode of preparation reduces cobalt content on the basis that keeps cobalt acid lithium performance advantage greatly.
The below enumerates several embodiment:
Embodiment 1:
According to Li
2CO
3Middle Li, Co
3O
4Molar ratio Li:Co=1.05:1 of middle Co carries out mixed grinding, and milling time is 3h; Mixed raw material is positioned in the baking furnace, is 3m in air mass flow
3Calcine in the atmosphere of/h, calcining heat is 970 ℃, and calcination time is 10h; Product after the step calcining as in the mixing tank, is added SnO
2, Sn:Co=0.04:1, mixed grinding, milling time is 3h; The product that step is ground is positioned in the baking furnace, is 2m in air mass flow
3Calcine in the atmosphere of/h, calcining heat is 800 ℃, and calcination time is 10h, the lithium cobaltate cathode material of the Sn that obtains mixing.
Lithium ion battery lithium cobaltate cathode material even particle distribution, purity by embodiment 1 preparation is high, free from foreign meter, have intact degree of crystallinity, the battery of assembling discharges and recharges about 25 ℃, when the charging/discharging voltage scope was 2.7V～4.3V, the first discharge capacity of 0.2C rate charge-discharge was 159.6mAh/g.Indices test result such as Fig. 1, Fig. 2, Fig. 3.
According to Li
2CO
3Middle Li, Co
3O
4Molar ratio Li:Co=1.06:1 of middle Co carries out mixed grinding, and milling time is 3h; Mixed raw material is positioned in the baking furnace, is 3m in air mass flow
3Calcine in the atmosphere of/h, calcining heat is 980 ℃, and calcination time is 10h; Product after the calcining as in the mixing tank, is added SnO
2, Sn:Co=0.03:1, mixed grinding, milling time is 3h; The product that step is ground is positioned in the baking furnace, is 2m in air mass flow
3Calcine in the atmosphere of/h, calcining heat is 850 ℃, and calcination time is 10h, the lithium cobaltate cathode material of the Sn that obtains mixing.
Lithium ion battery lithium cobaltate cathode material even particle distribution, purity by embodiment 2 preparation is high, free from foreign meter, have intact degree of crystallinity, the battery of assembling discharges and recharges about 25 ℃, when the charging/discharging voltage scope was 2.7V～4.3V, the first discharge capacity of 0.2C rate charge-discharge was 159.0mAh/g.
Embodiment 3
According to Li
2CO
3Middle Li, Co
3O
4Molar ratio Li:Co=1.06:1 of middle Co carries out mixed grinding, and milling time is 3h; Mixed raw material is positioned in the baking furnace, is 3m in air mass flow
3Calcine in the atmosphere of/h, calcining heat is 970 ℃, and calcination time is 10h; Product after the calcining as in the mixing tank, is added SnO
2, Sn:Co=0.05:1, mixed grinding, milling time is 3h; The product that step is ground is positioned in the baking furnace, is 2m in air mass flow
3Calcine in the atmosphere of/h, calcining heat is 800 ℃, and calcination time is 10h, the lithium cobaltate cathode material of the Sn that obtains mixing.
Lithium ion battery lithium cobaltate cathode material even particle distribution, purity by embodiment 3 preparation is high, free from foreign meter, have intact degree of crystallinity, the battery of assembling discharges and recharges about 25 ℃, when the charging/discharging voltage scope was 2.7V～4.3V, the first discharge capacity of 0.2C rate charge-discharge was 157.1mAh/g.
Claims (3)
1. anode material for lithium-ion batteries tin dope type cobalt acid lithium and preparation method thereof, it is characterized in that: cobalt compound and lithium compound are mixed in proportion, and it is synthetic that first time carried out at high temperature calcining, and the cobalt acid lithium that obtains is ground, and obtains A and expect; Take tin compound and A material as raw material mixes in proportion, mixing rear calcining, to carry out second time synthetic, and the sour lithium of cobalt of tin dope is ground, and obtains finished product.
2. a kind of anode material for lithium-ion batteries tin dope type cobalt acid lithium according to claim 1 and preparation method thereof, it is characterized in that: the molar ratio of described lithium compound and cobalt compound is Li/Co=1.00～1.06/1.00, and tin compound and cobalt compound molar ratio are Sn/Co=0.03～0.05/1.00; Described incorporation time is 2～3 hours.
3. a kind of anode material for lithium-ion batteries tin dope type cobalt acid lithium according to claim 1 and preparation method thereof, it is characterized in that: described calcining heat is 800～980 ℃, 9～11 hours time, pass into air in the calcination process, flow is 2～3m
3/ h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105489833A CN103000881A (en) | 2012-12-18 | 2012-12-18 | Positive material, namely tin-doped lithium cobalt oxide, for lithium ion cell, and preparation method of positive material |
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| CN2012105489833A CN103000881A (en) | 2012-12-18 | 2012-12-18 | Positive material, namely tin-doped lithium cobalt oxide, for lithium ion cell, and preparation method of positive material |
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| CN2012105489833A Pending CN103000881A (en) | 2012-12-18 | 2012-12-18 | Positive material, namely tin-doped lithium cobalt oxide, for lithium ion cell, and preparation method of positive material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113526565A (en) * | 2021-07-09 | 2021-10-22 | 天津大学 | Method for rapidly synthesizing lithium cobaltate cathode material and application |
| CN114388772A (en) * | 2021-12-09 | 2022-04-22 | 格力钛新能源股份有限公司 | Molybdenum vanadium titanium niobium composite oxide negative electrode material, preparation method thereof and lithium ion battery |
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| CN101694874A (en) * | 2009-10-21 | 2010-04-14 | 南通瑞翔新材料有限公司 | Process for preparing lithium cobalt oxide of lithium-ion secondary battery cathode materials |
| CN101880066A (en) * | 2010-06-21 | 2010-11-10 | 中信国安盟固利电源技术有限公司 | Preparation method of high-density high-safety long-life lithium cobaltate |
| CN102244232A (en) * | 2010-05-13 | 2011-11-16 | 天津华夏泓源实业有限公司 | Method for preparing composite lithium cobaltate anode material with high capacity and high compact density |
| CN102368552A (en) * | 2011-10-17 | 2012-03-07 | 江苏科捷锂电池有限公司 | High-performance anode material lithium cobalt oxide of lithium ion battery and preparation method thereof |
-
2012
- 2012-12-18 CN CN2012105489833A patent/CN103000881A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101694874A (en) * | 2009-10-21 | 2010-04-14 | 南通瑞翔新材料有限公司 | Process for preparing lithium cobalt oxide of lithium-ion secondary battery cathode materials |
| CN102244232A (en) * | 2010-05-13 | 2011-11-16 | 天津华夏泓源实业有限公司 | Method for preparing composite lithium cobaltate anode material with high capacity and high compact density |
| CN101880066A (en) * | 2010-06-21 | 2010-11-10 | 中信国安盟固利电源技术有限公司 | Preparation method of high-density high-safety long-life lithium cobaltate |
| CN102368552A (en) * | 2011-10-17 | 2012-03-07 | 江苏科捷锂电池有限公司 | High-performance anode material lithium cobalt oxide of lithium ion battery and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113526565A (en) * | 2021-07-09 | 2021-10-22 | 天津大学 | Method for rapidly synthesizing lithium cobaltate cathode material and application |
| CN114388772A (en) * | 2021-12-09 | 2022-04-22 | 格力钛新能源股份有限公司 | Molybdenum vanadium titanium niobium composite oxide negative electrode material, preparation method thereof and lithium ion battery |
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Application publication date: 20130327 |