CN102751484A - Preparation method for cobaltosic oxide electrode material having one-dimensional nanometer chain structure or spherical structure - Google Patents
Preparation method for cobaltosic oxide electrode material having one-dimensional nanometer chain structure or spherical structure Download PDFInfo
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- CN102751484A CN102751484A CN2012100522661A CN201210052266A CN102751484A CN 102751484 A CN102751484 A CN 102751484A CN 2012100522661 A CN2012100522661 A CN 2012100522661A CN 201210052266 A CN201210052266 A CN 201210052266A CN 102751484 A CN102751484 A CN 102751484A
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Abstract
The present invention relates to a preparation method for a cobaltosic oxide electrode material, and application research thereof, wherein the cobaltosic oxide (Co3O4) is a lithium ion negative electrode material having a one-dimensional nanometer chain structure or a spherical structure. According to the present invention, a hydrothermal method and a thermal decomposition method are combined to achieve controllable preparation of a nanometer pearl necklace-like cobaltosic oxide; the method has advantages of low process cost, short time, good product stability, and the like, and is applicable for industrial production; results show that: spherical nanoparticles having rough surfaces have large specific surface areas so as to increase a contact area between a lithium ion active substance and the electrode, and significantly improve rate charging/discharging capacity of the lithium-ion battery; and the Co3O4 having the one-dimensional nanometer chain structure further has good electric conductivity and large comparison area so as to reduce electrode sheet resistance and internal resistance of the battery and provide good application prospects in the lithium ion battery.
Description
[technical field]: the invention belongs to the lithium ion battery production technical field, particularly a kind of preparation method of lithium ion battery negative material.
[background technology]: lithium ion battery is widely used in fields such as mobile communication, portable electric appts, electric tool, electric bicycle electric automobile owing to have voltage height, energy density height, memory-less effect, advantage such as pollution-free.At present, commercial lithium ion battery normally with materials such as cobalt acid lithium, LiMn2O4, nickle cobalt lithium manganate, LiFePO4s as positive electrode, with graphite, soft carbon, hard carbon as negative material; But because a theoretical specific capacity 372mAh/g of material with carbon element, actual performance capacity is on the low side, has limited the further lifting of capacity of lithium ion battery.And in containing the organic electrolyte of PC base, be very easy to take place solvent and the common embedding of lithium ion in graphite linings and cause that graphite linings peels off, negative pole structure is destroyed, thereby causes the cycle performance of battery and the quick decay of security performance.
It is thus clear that negative material plays an important role to capacity, performance and the fail safe of battery in lithium ion battery; Therefore the negative material of developing high power capacity, high security is the effective way that improves the lithium ion battery performance.Characteristics such as the oxide of transition metals cobalt has the theoretical specific capacity height, and synthetic method is simple are a kind of very desirable lithium ion battery negative materials.And the embedding lithium plateau potential of cobaltosic oxide is higher, can effectively prevent the generation of lithium metal dendrite in charge and discharge process, prevents the generation of internal short-circuit, thereby improves the fail safe of lithium ion battery greatly.At present, about cobaltosic oxide as the existing a lot of relevant report of the negative material of lithium ion battery.Like Wei-Yang Li, Li-Na Xu, andJun Chen, Co
3O
4Nanomaterials in lithium-ion batteries and gas sensors, Adv.Funct.Mater.2005,15,851-857 has reported that the synthetic cobaltosic oxide nano-tube of employing template uses negative material as lithium ion battery; The specific capacity of discovering cobaltosic oxide reaches more than the 800mAh/g, and the capacity＞nanometer rods of nano tube structure＞nano particle, and the specific capacity that increases specific area and help improving cobaltosic oxide, the effective rate of utilization that improves material are described.In addition, one-dimensional nano structure helps improving the conductivity of material between conductivity on the one dimension direction and increase particle, the performance performance that finally improves electrode material.
But; Synthetic at present cobaltosic oxide adopts methods such as sol-gel process and high temperature solid-state decomposition more; Synthesis cycle is longer, and product is generally irregular particle or larger-size bulk, and its size reaches several even tens microns; Cause the product specific capacity lower, and be unfavorable for that high power discharges and recharges.Therefore, patent of the present invention is explored synthetic simple nano novel structure preparation method of cobalt oxide, and it has crucial meaning.
[summary of the invention]: it is long to the objective of the invention is to solve the existing cobaltosic oxide preparation method cycle; Problems such as the product particle is bigger and irregular provide a kind of have the efficiently preparation method of cobalt oxide of 1-dimention nano chain structure and spherical structure and the application in lithium ion battery thereof.
[technical scheme of the present invention]:
The invention provides the preparation method of 1-dimention nano chain structure and spherical structure cobaltosic oxide electrode material, it is to adopt hydrothermal method and thermolysis process to combine, and realizes through following step:
1) at room temperature; The aqueous solution of 0.1～3.0mol/L that cobalt nitrate or cobalt chloride or cobaltous sulfate are configured to; Add polyvinylpyrrolidone (PVP) (molecular weight is 10000 or 40000) or ethylene glycol; To solution in gradually add the solution of ammonium carbonate or ammoniacal liquor at 1: 1 by cobalt ions and ammonium radical ion mol ratio then, and stir, generate suspension-turbid liquid;
2) above-mentioned suspension-turbid liquid is changed over to have in the teflon-lined hydrothermal reaction kettle, react 3～36 hours reaction time under 120～210 ℃ of conditions;
3) be cooled to room temperature after reaction finishes, use the deionized water wash product;
4) will wash afterproduct is transferred in the high temperature furnace; In air atmosphere under 300～700 ℃ of temperature conditions of high temperature; Sintering reaction 2～12 hours treats that temperature is cooled to room temperature, obtains having the oxide electrode material of the transition metals cobalt of 1-dimention nano chain structure or spherical structure.
The oxide electrode material of said transition metals cobalt is a cobaltosic oxide.
Said cobaltosic oxide is that spherical surface is coarse or peart necklace shaped; And the grain size of product and shape are adjustable, can obtain 1-dimention nano chain structure or the spherical structure electrode material of grain size at 50nm～2000nm through the temperature of adjustment hydro-thermal reaction and the concentration of reaction solution.
[advantage of the present invention and effect]: the present invention has following plurality of advantages: compare with template, synthetic method is simple, does not need template, and cost is lower; Same step high temperature solid-state method is compared; The gentle product particle diameter that obtains of precursor reaction condition is less; Specific area is higher, can significantly improve the diffusive migration speed of electronics and ion, and has 1-dimention nano chain structure or spherical structure through the synthetic product of the induction of surfactant; Increase the conductivity of active material, be beneficial to and reduce the internal resistance of cell.
The method that patent of the present invention provides employing hydro-thermal-thermal decomposition to combine can be synthesized the cobaltosic oxide electrode material with 1-dimention nano chain structure or spherical structure, and this method technology is simple, flow process short, constant product quality and be easy to suitability for industrialized production; Be particularly suitable for preparing lithium ion battery and use negative material.
[description of drawings]:
Fig. 1 is the X-ray powder diffraction figure of the cobaltosic oxide nano material that makes according to embodiment 1;
Fig. 2 is for making the sem photograph of the cobaltosic oxide nano material of 1-dimention nano chain according to embodiment 1;
Fig. 3 is for making the sem photograph of the cobaltosic oxide nano material of spherical structure according to embodiment 2.
[embodiment]:
Embodiment 1: the preparation of the peart necklace shaped cobaltosic oxide of 1-dimention nano
At ambient temperature, with CoCl
26H
2O is configured to the aqueous solution of 0.1mol/L, measures 15mL, to the polyvinylpyrrolidone that wherein adds 1mL 0.01mol/L (PVP) solution, stirs, with NH
4(0.1mol/L, 15mL) aqueous solution slowly is added drop-wise to above-mentioned CoCl to OH
26H
2Go in the aqueous solution of O, fully stir, just have the aubergine deposition to generate, drip off continued and stirred 10 minutes, it was in the stainless steel hydrothermal reaction kettle of liner that aubergine suspension is moved into the 50mL polytetrafluoroethylene, in 160 ℃ of reactions 4 hours.After finishing, reaction is cooled to room temperature; With deionized water wash 3 times, deposition is transferred in the crucible, be placed on high-temperature cabinet 400 ℃ of constant temperature 4 hours; Treat the temperature natural cool to room temperature, obtain having the electrode material of the cobaltosic oxide of the peart necklace shaped structure of 1-dimention nano.The chemical equation of this reaction is:
The XRD spectra of the cobaltosic oxide of described method preparation is as shown in Figure 1; Its diffraction maximum and standard card fit like a glove, and other diffraction maximum do not occur, explain that the cobaltosic oxide purity that obtains is very high.
As shown in Figure 2 the showing of stereoscan photograph of the cobaltosic oxide with 1-dimention nano pearl necklace structure of described method preparation: the peart necklace shaped structure that product is combined and formed by the shaggy spheric granules of a large amount of diameters between 300～500nm.
Embodiment 2: the preparation of spherical structure cobaltosic oxide
At ambient temperature, with Co (NO
3)
26H
2O is configured to the aqueous solution of 1mol/L, measures 15mL, and to wherein adding 2mL, the polyvinylpyrrolidone of 0.06mol/L (PVP) solution stirs, with NH
4(1mol/L, 15mL) aqueous solution slowly is added drop-wise to above-mentioned Co (NO to OH
3)
26H
2Go in the aqueous solution of O, fully stir, have the aubergine deposition to generate, drip off continued and stirred 10 minutes, it was in the stainless steel still of liner that aubergine suspension is moved into the 50mL polytetrafluoroethylene, in 180 ℃ of reactions 4 hours.Reaction is cooled to room temperature after finishing, and with deionized water wash 3 times, deposition is transferred in the crucible, is placed on high-temperature cabinet 400 ℃ of constant temperature 4 hours, treats the temperature natural cool to room temperature, obtains the electrode material of spherical cobaltic-cobaltous oxide.
The stereoscan photograph of the spherical cobaltic-cobaltous oxide of described method preparation is as shown in Figure 3, and product is that spheric granules and the surface of particle diameter about 1 μ m is more coarse.
Claims (3)
1. the invention provides the preparation method of 1-dimention nano chain structure and spherical structure cobaltosic oxide electrode material, it is to adopt hydrothermal method and thermolysis process to combine, and realizes through following step:
1) at room temperature; The aqueous solution of 0.1～3.0mol/L that cobalt nitrate or cobalt chloride or cobaltous sulfate are configured to; Add polyvinylpyrrolidone (PVP) (molecular weight is 10000 or 40000) or ethylene glycol; To solution in gradually add the solution of ammonium carbonate or ammoniacal liquor at 1: 1 by cobalt ions and ammonium radical ion mol ratio then, and stir, generate suspension-turbid liquid;
2) above-mentioned suspension-turbid liquid is changed over to have in the teflon-lined hydrothermal reaction kettle, react 3～36 hours reaction time under 120～210 ℃ of conditions;
3) be cooled to room temperature after reaction finishes, use the deionized water wash product;
4) will wash afterproduct is transferred in the high temperature furnace; In air atmosphere under 300～700 ℃ of temperature conditions of high temperature; Sintering reaction 2～12 hours treats that temperature is cooled to room temperature, obtains having the oxide electrode material of the transition metals cobalt of 1-dimention nano chain structure or spherical structure.
2. the oxide electrode material according to the said transition metals cobalt of claim 1 is a cobaltosic oxide.
3. be that spherical surface is coarse or peart necklace shaped according to the said cobaltosic oxide of claim 2; And the grain size of product and shape are adjustable, can obtain 1-dimention nano chain structure or the spherical structure electrode material of grain size at 50nm～2000nm through the temperature of adjustment hydro-thermal reaction and the concentration of reaction solution.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224258A (en) * | 2013-04-26 | 2013-07-31 | 吉林化工学院 | Simple method for preparing Co3O4 nano-spheres and beta-Co(OH)2 micron-flowers |
| CN104209126A (en) * | 2014-09-25 | 2014-12-17 | 四川理工学院 | Preparation method of bunchy prism cobaltosic oxide |
| CN104775185A (en) * | 2015-04-14 | 2015-07-15 | 济南大学 | Cobaltosic oxide bead-chain-shaped fiber and preparation method thereof |
| CN104876284A (en) * | 2015-04-17 | 2015-09-02 | 济南大学 | Nano bead chain cobaltosic oxide and preparation method thereof |
| CN105381800A (en) * | 2014-09-09 | 2016-03-09 | 中国科学院大连化学物理研究所 | Non-noble metal oxide combustion catalyst, and preparation method and use thereof |
| CN106159157A (en) * | 2015-04-13 | 2016-11-23 | 北京化工大学 | The preparation method of a kind of ceramics polymer composite diaphragm, this ceramics polymer composite diaphragm and application thereof |
| CN108383172A (en) * | 2018-05-30 | 2018-08-10 | 上海师范大学 | A kind of preparation method of cobaltosic oxide nano ball |
| CN109081378A (en) * | 2018-06-28 | 2018-12-25 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七二研究所） | A kind of preparation method and product of ion cathode material lithium |
| CN112537797A (en) * | 2020-12-07 | 2021-03-23 | 安徽师范大学 | Ferroferric oxide/carbon nano tube/sulfur-loaded composite material with one-dimensional chain-like core-shell structure, preparation method and application |
| CN113896250A (en) * | 2021-09-30 | 2022-01-07 | 广州发展新能源股份有限公司 | Layered Co3O4Lithium ion battery cathode material and preparation method thereof |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224258A (en) * | 2013-04-26 | 2013-07-31 | 吉林化工学院 | Simple method for preparing Co3O4 nano-spheres and beta-Co(OH)2 micron-flowers |
| CN105381800A (en) * | 2014-09-09 | 2016-03-09 | 中国科学院大连化学物理研究所 | Non-noble metal oxide combustion catalyst, and preparation method and use thereof |
| CN104209126A (en) * | 2014-09-25 | 2014-12-17 | 四川理工学院 | Preparation method of bunchy prism cobaltosic oxide |
| CN104209126B (en) * | 2014-09-25 | 2016-05-25 | 四川理工学院 | A kind of preparation method of pencil prism cobaltosic oxide |
| CN106159157B (en) * | 2015-04-13 | 2018-11-16 | 北京化工大学 | A kind of preparation method of ceramics polymer composite diaphragm, the ceramics polymer composite diaphragm and its application |
| CN106159157A (en) * | 2015-04-13 | 2016-11-23 | 北京化工大学 | The preparation method of a kind of ceramics polymer composite diaphragm, this ceramics polymer composite diaphragm and application thereof |
| CN104775185B (en) * | 2015-04-14 | 2017-02-22 | 济南大学 | Cobaltosic oxide bead-chain-shaped fiber and preparation method thereof |
| CN104775185A (en) * | 2015-04-14 | 2015-07-15 | 济南大学 | Cobaltosic oxide bead-chain-shaped fiber and preparation method thereof |
| CN104876284A (en) * | 2015-04-17 | 2015-09-02 | 济南大学 | Nano bead chain cobaltosic oxide and preparation method thereof |
| CN108383172A (en) * | 2018-05-30 | 2018-08-10 | 上海师范大学 | A kind of preparation method of cobaltosic oxide nano ball |
| CN109081378A (en) * | 2018-06-28 | 2018-12-25 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七二研究所） | A kind of preparation method and product of ion cathode material lithium |
| CN112537797A (en) * | 2020-12-07 | 2021-03-23 | 安徽师范大学 | Ferroferric oxide/carbon nano tube/sulfur-loaded composite material with one-dimensional chain-like core-shell structure, preparation method and application |
| CN112537797B (en) * | 2020-12-07 | 2023-04-18 | 安徽师范大学 | Ferroferric oxide/carbon nano tube/sulfur-loaded composite material with one-dimensional chain-like core-shell structure, preparation method and application |
| CN113896250A (en) * | 2021-09-30 | 2022-01-07 | 广州发展新能源股份有限公司 | Layered Co3O4Lithium ion battery cathode material and preparation method thereof |
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