CN1808747A - Positive electrode material (LiCoO2) of lithium ion cell and its preparation method - Google Patents
Positive electrode material (LiCoO2) of lithium ion cell and its preparation method Download PDFInfo
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- CN1808747A CN1808747A CNA2006100002252A CN200610000225A CN1808747A CN 1808747 A CN1808747 A CN 1808747A CN A2006100002252 A CNA2006100002252 A CN A2006100002252A CN 200610000225 A CN200610000225 A CN 200610000225A CN 1808747 A CN1808747 A CN 1808747A
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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 LiCoO2 material for lithium ion battery positive pole and its preparing process, which employs a die plate agent method using poly epoxyethane, poly epoxypropane and poly epoxyethane as the soft die plate, the obtained LiCoO2 material has a single-crystal structure and a nanometer level grain size.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of lithium ion cell positive LiCoO
2Preparation methods.The material of preparation has mono-crystalline structures, and particle diameter is a nanoscale, and specific capacity height, stable cycle performance, is applicable to liquid state or polymer Li-ion battery.
Background technology
Lithium ion battery is since 1991 put on market, and its performance significantly improves, application constantly enlarges.But the positive electrode of lithium ion battery still is mainly LiCoO on the market
2, this depends primarily on LiCoO
2Excellent electrochemical performance.
Traditional LiCoO
2The preparation method is a high-temperature solid phase reaction method, and the material pattern is irregular, particle is big, the preparation difficulty of chemical dosage ratio because the mixing of machinery and long high-temperature calcination cause to adopt this method.And other softening length of schooling Preparation Method, as sol-gel method (G.T.Fey, K.S.Chen, B.J.Hwang, Y.L.Lin J.Power Sources 68 (1997) 519), co-deposition method (M.Yoshio, H.Tanaka, K.Tominaga, H.Noguchi, J.Power Sources 40 (1992) 347) and Rotary drying method (S.-T.Myung, H.-T.Chung, J.Power Sources 84 (1999) 32) can overcome above shortcoming, prepare nano level LiCoO
2Material, but this nano level LiCoO
2Dispersiveness is still not ideal enough, and does not have mono-crystalline structures.
Triblock copolymer P (EO)-P (PO)-P (EO), it is poly(ethylene oxide)-PPOX-poly(ethylene oxide), be soft template (the Dongyuan Zhao for preparing order mesoporous or nano material, Jianglin Feng, Qisheng Huo, Nicholas Melosh, Glenn H.Fredrickson, Bradley F.Chmelka, Galen D.Stucky, Science 279 (1998) 548).But be used to prepare lithium ion cell positive LiCoO
2The preparation of material does not but appear in the newspapers.
Summary of the invention
The object of the present invention is to provide a kind of novel lithium ion cell positive LiCoO
2Material, this material are monocrystal material.
Another object of the present invention also is to provide a kind of lithium ion cell positive LiCoO
2The preparation method, this method is a template with the block copolymer, prepares to have mono-crystalline structures, particle diameter is the LiCoO of nano level capacity height, stable cycle performance
2
A kind of lithium ion cell positive LiCoO
2Material, this LiCoO
2Material adopts template agent method to make, and has mono-crystalline structures.
Lithium ion cell positive LiCoO of the present invention
2The preparation method of monocrystal material, its concrete steps are as follows:
(1) will prepare LiCoO
2Raw material cobalt compound and lithium compound be dissolved in alcohol or the water;
(2) adding the triblock copolymer surfactant in solution is soft template, and then heating boils off solvent;
(3) will remove the solid matter that obtains behind the solvent and grind, and, behind the cool to room temperature, grind, and sieve with sub-sieve 300～800 ℃ of temperature lower calcinations 4～24 hours.
In the above-mentioned steps (2), described triblock copolymer surfactant is general formula copolymer p (EO)
n-P (PO)
m-P (EO)
k, wherein the value of n, m, k is all between 5 to 200.
Described cobalt compound can be used for preparing LiCoO for all
2Cobalt compound, can be in Cobalt diacetate tetrahydrate, cobalt chloride, CoCL2, cobalt nitrate hexahydrate, sulfuric acid monohydrate cobalt, the cobalt sulfate any one or more usually.
Described lithium compound can be used for preparing LiCoO for all
2Lithium compound, can be in lithium chloride, lithium carbonate, lithium acetate, lithium nitrate, nitrate trihydrate lithium, lithium sulfate, sulfuric acid monohydrate lithium, the Lithium hydroxide monohydrate any one or more usually.
Described alcohol can be methyl alcohol, ethanol, propyl alcohol, butanols, 1,2-propylene glycol, 2, ammediol, 2, any one or more in 3-butanediol, isopropyl alcohol, the isobutanol.
Preferable mode is that the molecular weight of described template is between 1000～30000.
Adopt the anode LiCoO of method preparation of the present invention
2Material is owing to adopt triblock copolymer surfactant poly(ethylene oxide)-PPOX-poly(ethylene oxide) (P (EO)
n-P (PO)
m-P (EO)
k) as soft template, synthetic LiCoO
2, because the self-assembly property and the template action of this surfactant, Zhi Bei LiCoO by this method
2Not only its particle diameter reaches nanoscale, and the product that makes is monocrystal material and good dispersion, has the advantage of specific capacity height, stable cycle performance, is applicable to liquid state or polymer Li-ion battery.
Description of drawings
Fig. 1 is the LiCoO that utilizes the present invention to prepare
2X-ray diffractogram of powder.
Fig. 2 is the LiCoO that utilizes preparation in the embodiment of the invention 3
2Be assembled into the first charge-discharge curve of 2025 type button cells with lithium metal.
Fig. 3 is the LiCoO that utilizes preparation in the embodiment of the invention 3
2Be assembled into the cycle performance figure of 2025 type button cells with lithium metal.
Embodiment
The invention will be further described below in conjunction with the drawings and specific embodiments.
Embodiment 1:
At first (be cobalt chloride: lithium chloride is 1: 1 or is about 1: 1 with cobalt chloride, the lithium chloride of stoichiometric proportion, for example be 1: 1-1.05) water-soluble, the consumption of aqueous solvent guarantees to be enough to dissolve cobalt chloride and lithium chloride gets final product, and adding soft template P123 again in solution (is P (EO)
20-P (PO)
70-P (EO)
20), heating boils off solvent then, grinds, and earlier 300 ℃ of calcinings 4 hours, at last in 600 ℃ of calcinings 12 hours, is cooled to take out after the room temperature and grinds, and crosses 300 order sub-sieves, can make LiCoO
2, its X-ray powder diffraction pattern is seen Fig. 1, sem photograph SEM demonstration product average grain diameter, is utilized the Scherrer formula to calculate product average crystalline particle diameter and is 64.9nm according to the X-ray powder diffraction pattern at 60-70nm.Two results' the consistent product that shows is a mono-crystalline structures.
Embodiment 2:
At first cobalt nitrate hexahydrate, the nitrate trihydrate lithium with stoichiometric proportion is dissolved in ethanol, and make the concentration of two kinds of nitrate reach 0.1-0.3M, toward wherein adding template P123, its addition is 0.001-0.015M, heating then, boil off solvent, grind, earlier 300 ℃ of calcinings 4 hours, at last in 700 ℃ of calcinings 24 hours, take out grinding after being cooled to room temperature, cross 300 order sub-sieves, can make LiCoO
2, its Scanning Electron Microscope photos reveal product average grain diameter is 70-80nm, is nanoscale, and is similarly monocrystal material.
Embodiment 3:
At first Cobalt diacetate tetrahydrate, CoCL2, lithium acetate, the lithium chlorate with stoichiometric proportion is dissolved in ethanol (but mixture of ethanol, propyl alcohol), is P (EO) toward wherein adding template P85
26-P (PO)
39-P (EO)
26) heating then, boil off solvent, grind, earlier 300 ℃ of calcinings 4 hours,, be cooled to take out after the room temperature and grind at last in 750 ℃ of calcinings 10 hours, cross 300 order sub-sieves, can make LiCoO
2, average grain diameter is about 80nm.
The material that makes is made CR2025 type button Experimental cell, with the charging and discharging currents of 0.2C, charge and discharge in the 2.5-4.3V scope, temperature is 25 ℃.Its chemical property is seen Fig. 2 and Fig. 3.By Fig. 2 and Fig. 3 as can be seen, its specific capacity height, stable cycle performance.
Claims (7)
1, a kind of lithium ion cell positive LiCoO
2Material is characterized in that: this LiCoO
2Material adopts template agent method to make, and has mono-crystalline structures.
2, the described lithium ion cell positive LiCoO of a kind of claim 1
2The preparation method, it is characterized in that this method comprises the steps:
(1) will prepare LiCoO
2Raw material cobalt compound and lithium compound be dissolved in alcohol or the water;
(2) adding the triblock copolymer surfactant in solution is soft template, and then heating boils off solvent;
(3) will remove the solid matter that obtains behind the solvent and grind, and, behind the cool to room temperature, grind, and sieve with sub-sieve 300～800 ℃ of temperature lower calcinations 4～24 hours.
3, lithium ion cell positive LiCoO as claimed in claim 2
2The preparation method, it is characterized in that: in the above-mentioned steps (2), described triblock copolymer surfactant is following general formula copolymer
P(EO)
n-P(PO)
m-P(EO)
k
Wherein the value of n, m, k is all between 5 to 200.
4, lithium ion cell positive LiCoO as claimed in claim 3
2The preparation method, it is characterized in that: described molecular weight of copolymer is between 1000～30000.
5, as described lithium ion cell positive LiCoO one of in the claim 2 to 4
2The preparation method, it is characterized in that: described cobalt compound is any one or more in Cobalt diacetate tetrahydrate, cobalt chloride, CoCL2, cobalt nitrate hexahydrate, sulfuric acid monohydrate cobalt, the cobalt sulfate.
6, as described lithium ion cell positive LiCoO one of in the claim 2 to 4
2The preparation method, it is characterized in that: described lithium compound is any one or more in lithium chloride, lithium carbonate, lithium acetate, lithium nitrate, nitrate trihydrate lithium, lithium sulfate, sulfuric acid monohydrate lithium, the Lithium hydroxide monohydrate.
7, as described lithium ion cell positive LiCoO one of in the claim 2 to 4
2The preparation method, it is characterized in that: described alcohol is methyl alcohol, ethanol, propyl alcohol, butanols, 1,2-propylene glycol, 2, ammediol, 2, any one or more in 3-butanediol, isopropyl alcohol, the isobutanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006100002252A CN1808747A (en) | 2006-01-06 | 2006-01-06 | Positive electrode material (LiCoO2) of lithium ion cell and its preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006100002252A CN1808747A (en) | 2006-01-06 | 2006-01-06 | Positive electrode material (LiCoO2) of lithium ion cell and its preparation method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101807689A (en) * | 2010-04-28 | 2010-08-18 | 复旦大学 | Lithium ion battery electrode material and preparation method thereof |
| WO2010091611A1 (en) * | 2009-02-13 | 2010-08-19 | 成都晶元新材料技术有限公司 | Ni-, co- and mn- multi-doped positive material for lithium ion battery and preparation method thereof |
| CN104415015A (en) * | 2013-09-03 | 2015-03-18 | 于杰 | Poison-drawing-out dressing |
| CN110474085A (en) * | 2019-08-12 | 2019-11-19 | 深圳市科瑞隆科技有限公司 | High temperature modification high-voltage lithium ion batteries and preparation method thereof |
| US10818976B2 (en) | 2016-06-29 | 2020-10-27 | International Business Machines Corporation | Rechargeable battery |
-
2006
- 2006-01-06 CN CNA2006100002252A patent/CN1808747A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010091611A1 (en) * | 2009-02-13 | 2010-08-19 | 成都晶元新材料技术有限公司 | Ni-, co- and mn- multi-doped positive material for lithium ion battery and preparation method thereof |
| CN101807689A (en) * | 2010-04-28 | 2010-08-18 | 复旦大学 | Lithium ion battery electrode material and preparation method thereof |
| CN104415015A (en) * | 2013-09-03 | 2015-03-18 | 于杰 | Poison-drawing-out dressing |
| US10818976B2 (en) | 2016-06-29 | 2020-10-27 | International Business Machines Corporation | Rechargeable battery |
| CN110474085A (en) * | 2019-08-12 | 2019-11-19 | 深圳市科瑞隆科技有限公司 | High temperature modification high-voltage lithium ion batteries and preparation method thereof |
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