CN101928044B - Preparation method of nano cobaltosic oxide used for negative electrode material of lithium ion battery - Google Patents

Preparation method of nano cobaltosic oxide used for negative electrode material of lithium ion battery Download PDF

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CN101928044B
CN101928044B CN200910019235A CN200910019235A CN101928044B CN 101928044 B CN101928044 B CN 101928044B CN 200910019235 A CN200910019235 A CN 200910019235A CN 200910019235 A CN200910019235 A CN 200910019235A CN 101928044 B CN101928044 B CN 101928044B
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lithium ion
ion battery
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preparation
cobaltic
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CN101928044A (en
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王介强
牛锛
杜国栋
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University of Jinan
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a preparation method of nano cobaltosic oxide used for a negative electrode material of a lithium ion battery. The preparation method comprises the following steps: dissolving bivalent Co nitrate into water, and then adding urea to prepare a reaction solution, wherein the concentration of the bivalent Co ion is 0.1-0.2mol/L, and the mole ratio of the urea to the bivalent Co ion is 6-10:1; pouring the reaction solution in a hermetical reaction container to be placed in a microwave field for microwave irradiation, separating, washing and drying a generated precursor after the reaction is finished; and calcining the dried precursor in the air to obtain the nano cobaltosic oxide with the catenulate porous structure. The nano cobaltosic oxide is used for the negative electrode material of the lithium ion battery, and has excellent cycling property and good stability. The preparation method has the characteristics of simple process, low cost and no pollution.

Description

A kind of preparation method who can be used for the nano-cobaltic-cobaltous oxide of lithium ion battery negative material
Technical field
The present invention relates to a kind of preparation method who can be used for the nano-cobaltic-cobaltous oxide of lithium ion battery negative material, belong to field of inorganic nonmetallic material.
Background technology
Lithium ion battery becomes present good comprehensive properties battery system because of it has excellent characteristic, has become one of current with following important new forms of energy.Along with its Application Areas from civilian information industry (high energy portable electric appts such as mobile telephone, notebook computer) further expanding to energy traffic (electromobile etc.); Arrive the indispensable important energy source of national defense and military fields military equipment again, the capacity and the fast charging and discharging ability of lithium ion battery are all had higher requirement.Negative material is one of good and bad key factor of decision lithium ion battery over-all properties.Research to lithium ion battery negative material mainly concentrates on carbon material, oxide material and alloy material.At present; The subject matter that the commercialization carbon negative pole material exists is: actual specific capacity is low (to be about 300～330mAh/g; Theoretical specific capacity is 372mAh/g), big, the multiplying power discharging property difference of irreversible loss etc. first; And embedding lithium current potential is low, and graphite surface possibly cause the deposition of metallic lithium in charge and discharge process, has certain potential safety hazard.Therefore, trying to explore specific storage height, the capacity attenuation rate is little, safety performance is good new type lithium ion battery negative material system, has been the focus of research in the world.In the available negative material, oxide material has accounted for greatly, is more promising negative material.
People study as storage cathode of lithium material transition metal oxide in early days, like MoO 2, WO 2, TiO 2And Fe 2O 3Deng.But because of having a certain amount of irreversible capacity loss after the circulation of the 1st week, feasible research to them once was absorbed in low ebb.2000, the transition metal oxide MO (M=Co, Fe, Ni or Cu) to nanoscale on " nature " magazine such as Poizot reported as lithium ion battery negative material.Its chemical property of this type oxide of finding nanoscale obviously is different from conventional material, and reversible capacity between the 800mAh/g, and has high capability retention at 600mAh/g.Show that nano-metal-oxide at the lithium storage content that improves negative material, improves the cycle life aspect of lithium cell, shown certain advantage.
Reducing starting material and preparing method's cost, also is the requirement that lithium ion battery oxide cathode material is realized the marketization.
Chinese patent CN 1837066A discloses a kind of process for temperature-control pressure-control microwave synthesis of water soluble cobaltosic oxide nano crystal; This method is solvent with water; Cobalt salt is water-soluble, add water miscible sulfhydryl compound as stablizer, the mol ratio of control cobalt ion and water miscible sulfhydryl compound is 1: 10 to 1: 1; Regulator solution pH value to 5～12 obtain precursor solution.Then this precursor solution is placed airtight polytetrafluoroethyltank tank, but in the microwave reactor of temperature controllable and pressure control, react, synthetic rapidly cobaltosic oxide nano crystal.Present method synthetic cobaltosic oxide nano crystal has good water solubility, and cost is low, and characteristics such as percent crystallinity height do not relate to but the physicochemical property of gained nanometer cobalt oxide had, and how unknown the chemical property that particularly is applied to lithium ion battery negative material is.
Summary of the invention
The objective of the invention is to overcome that the lithium ion battery negative material specific storage is low, the shortcoming of cycle characteristics difference; A kind of preparation method who can be used for the nano-cobaltic-cobaltous oxide of lithium ion battery negative material is provided; When the nano-cobaltic-cobaltous oxide of the present invention's preparation is used for lithium ion battery negative material; Excellent cycle characteristics is arranged, satisfactory stability property.This preparation method has that technology is simple, cost is low, free of contamination characteristics.
The present invention is achieved through following technical scheme:
A kind of preparation method who can be used for the nano-cobaltic-cobaltous oxide of lithium ion battery negative material of the present invention, adopt following steps:
(1) analytically pure divalence cobalt nitrate salt is dissolved in the zero(ppm) water, adds urea and stirring then, be made into reaction soln, the concentration of divalent cobalt ion is 0.1～0.2mol/L, and the molar ratio of urea and divalent cobalt ion is 6～10: 1;
(2) above-mentioned reaction soln is poured in the sealable reaction vessel; Place microwave field to carry out microwave exposure, microwave frequency is 2.45GHz, and the reaction soln temperature is 100～120 ℃; Soaking time is 1～3 hour, and reaction finishes the back precursor that generates is separated, washs and drying;
(3) dried precursor is carried out calcination processing in air, calcining temperature is 300～400 ℃, and soaking time is 1～3 hour, and calcinate is nano-cobaltic-cobaltous oxide.
Described nano-cobaltic-cobaltous oxide has the porous nanometer structure of one-dimensional chain, and the diameter of porous chain is 60～100nm, has mesoporous characteristic, and the aperture is 10～20nm.When described nano-cobaltic-cobaltous oxide was used for lithium ion battery negative material, under 50mA/g～400mA/g charge-discharge velocity test condition, through 50 circulations, its specific storage remained on 900～1300mAh/g.
The present invention adopts microwave-assisted synthesis to obtain the precursor of special appearance, and further thermal treatment obtains having the tricobalt tetroxide material of one-dimensional chain porous nanometer structure to the gained precursor, and technology is simple, cost is low, pollution-free.When this tricobalt tetroxide material is used for lithium ion battery negative material; Discharge and recharge under the condition in two-forty and can keep higher specific storage; Excellent cycle characteristics is arranged, under the charge-discharge velocity test condition that increases successively, have satisfactory stability property, when charge-discharge velocity is reduced to 50mA/g; Its specific storage can be recovered fully, and specific storage is stabilized in 1300mAh/g; Under high charge-discharge speed 400mA/g test condition, through 50 circulations, its specific storage still can remain on 900mAh/g.
Description of drawings
Fig. 1 is the XRD figure spectrum of embodiment 1 products therefrom, and wherein X-coordinate is 2 θ diffraction angle, and ordinate zou is a diffraction intensity.
Fig. 2 is the field emission scanning electron microscope figure of embodiment 1 gained tricobalt tetroxide product.
Fig. 3 is the high-resolution-ration transmission electric-lens figure of embodiment 1 gained tricobalt tetroxide product.
Fig. 4 is the N of embodiment 1 gained nano-cobaltic-cobaltous oxide 2Absorption/desorption isothermal curve and BJH pore size distribution curve thereof, wherein Relative pressure is a relative pressure, Volume absorbed is an adsorptive capacity; Pore Diameter is the aperture; Pore Volume is a pore volume, and Adsorption is absorption, and Desorption is a desorption.
Fig. 5 is used for the cycle characteristics that lithium ion battery negative material records successively for embodiment 1 gained nano-cobaltic-cobaltous oxide under charge-discharge velocity 50mA/g, 200mA/g, 400mA/g, 800mA/g and 50mA/g; Wherein Cycle number is a cycle index; Capacity is a specific storage; Charge is charging, and Discharge is discharge.
Fig. 6 is used for the cycle characteristics of lithium ion battery negative material under big charge-discharge velocity for embodiment 1 gained nano-cobaltic-cobaltous oxide, and wherein Charging/discharging rate is a charge-discharge velocity.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is described in detail.
Embodiment 1
Take by weighing the analytically pure Co (NO of 12.22g earlier 3) 26H 2O is dissolved in the 200ml water, takes by weighing 20g urea again and joins in this solution, adds water and makes the solution total amount to 300ml, treats Co (NO through stirring 3) 26H 2After O and urea dissolve fully; The solution for preparing poured into place microwave field (microwave frequency is 2.45GHz) to carry out microwave exposure in the sealable reaction vessel; Solution temperature is controlled at 110 ℃, soaking time 1 hour, and reaction finishes the back precursor that generates is separated, washs and drying; Dried precursor is calcined in air, and calcining temperature is 350 ℃, soaking time 2 hours.
Embodiment 2
Take by weighing the analytically pure Co (NO of 12.22g earlier 3) 26H 2O is dissolved in the 200ml water, takes by weighing 15g urea again and joins in this solution, adds water and makes the solution total amount to 300ml, treats Co (NO through stirring 3) 26H 2After O and urea dissolve fully; The solution for preparing poured into place microwave field (microwave frequency is 2.45GHz) to carry out microwave exposure in the sealable reaction vessel; Solution temperature is controlled at 110 ℃, soaking time 1 hour, and reaction finishes the back precursor that generates is separated, washs and drying; Dried precursor is calcined in air, and calcining temperature is 350 ℃, soaking time 2 hours.
Embodiment 3
Take by weighing the analytically pure Co (NO of 12.22g earlier 3) 26H 2O is dissolved in the 200ml water, takes by weighing 25g urea again and joins in this solution, adds water and makes the solution total amount to 300ml, treats Co (NO through stirring 3) 26H 2After O and urea dissolve fully; The solution for preparing poured into place microwave field (microwave frequency is 2.45GHz) to carry out microwave exposure in the sealable reaction vessel; Solution temperature is controlled at 110 ℃, soaking time 1 hour, and reaction finishes the back precursor that generates is separated, washs and drying; Dried precursor is calcined in air, and calcining temperature is 350 ℃, soaking time 2 hours.
Embodiment 4
Take by weighing the analytically pure Co (NO of 12.22g earlier 3) 26H 2O is dissolved in the 200ml water, takes by weighing 20g urea again and joins in this solution, adds water and makes the solution total amount to 300ml, treats Co (NO through stirring 3) 26H 2After O and urea dissolve fully; The solution for preparing poured into place microwave field (microwave frequency is 2.45GHz) to carry out microwave exposure in the sealable reaction vessel; Solution temperature is controlled at 110 ℃, soaking time 1 hour, and reaction finishes the back precursor that generates is separated, washs and drying; Dried precursor is calcined in air, and calcining temperature is 400 ℃, soaking time 2 hours.
Embodiment 5
Take by weighing the analytically pure Co (NO of 12.22g earlier 3) 26H 2O is dissolved in the 200ml water, takes by weighing 20g urea again and joins in this solution, adds water and makes the solution total amount to 300ml, treats Co (NO through stirring 3) 26H 2After O and urea dissolve fully; The solution for preparing poured into place microwave field (microwave frequency is 2.45GHz) to carry out microwave exposure in the sealable reaction vessel; Solution temperature is controlled at 110 ℃, soaking time 2 hours, and reaction finishes the back precursor that generates is separated, washs and drying; Dried precursor is calcined in air, and calcining temperature is 350 ℃, soaking time 2 hours.
Embodiment 6
Take by weighing the analytically pure Co (NO of 12.22g earlier 3) 26H 2O is dissolved in the 200ml water, takes by weighing 25g urea again and joins in this solution, adds water and makes the solution total amount to 300ml, treats Co (NO through stirring 3) 26H 2After O and urea dissolve fully; The solution for preparing poured into place microwave field (microwave frequency is 2.45GHz) to carry out microwave exposure in the sealable reaction vessel; Solution temperature is controlled at 115 ℃, soaking time 1 hour, and reaction finishes the back precursor that generates is separated, washs and drying; Dried precursor is calcined in air, and calcining temperature is 320 ℃, soaking time 2 hours.
Fig. 1-6 is for characterizing the picture of gained to the product of embodiment 1 gained.Wherein, Fig. 1 is the XRD figure spectrum of product, and the spectral line No.74-2120 of tricobalt tetroxide that has cubic crystal structure in this spectral line and the JCPDS DB is very identical, shows that this invents prepared product is monophasic tricobalt tetroxide; Fig. 2 and Fig. 3 show that prepared tricobalt tetroxide has the porous nanometer structure of one-dimensional chain; The diameter of porous chain is 80nm, and the result among Fig. 4 confirms that further gained nano chain tricobalt tetroxide has mesoporous characteristic, is distributed in about 13nm in the set of dimensions in hole.Can find out that from Fig. 5 and Fig. 6 this material has satisfactory stability property under the charge-discharge velocity test condition that increases successively, charge-discharge velocity is reduced to 50mA/g, and its specific storage can be recovered fully, and specific storage is stabilized in 1300mAh/g; Under high charge-discharge speed 400mA/g test condition, through 50 circulations, its specific storage still can remain on 900mAh/g.
Embodiment 2-6 products therefrom is characterized; All obtain the test result close with embodiment 1, all as shown in Figure 1 like the XRD figure of embodiment 2,3,4,5,6 products therefroms, illustrative embodiment 2-6 all makes tricobalt tetroxide; The diameter of the cobaltosic oxide porous chain of gained is 60～100nm; The aperture is 10～20nm, when it is used for lithium ion battery negative material, under the different charge-discharge velocity test conditions of 50mA/g～400mA/g; Through 50 circulations, its specific storage all remains on 900～1300mAh/g.

Claims (2)

1. preparation method who can be used for the nano-cobaltic-cobaltous oxide of lithium ion battery negative material is characterized in that adopting following steps:
(1) analytically pure divalence cobalt nitrate salt is dissolved in the zero(ppm) water, adds urea and stirring then, be made into reaction soln, the concentration of divalent cobalt ion is 3055/21828mol/L, and the molar ratio of urea and divalent cobalt ion is 6～10: 1;
(2) above-mentioned reaction soln is poured in the sealable reaction vessel; Place microwave field to carry out microwave exposure, microwave frequency is 2.45GHz, and the reaction soln temperature is 100 ℃; Soaking time is 1 hour, and reaction finishes the back precursor that generates is separated, washs and drying;
(3) dried precursor is carried out calcination processing in air, calcining temperature is 350 ℃, and soaking time is 2 hours, and calcinate is nano-cobaltic-cobaltous oxide;
When described nano-cobaltic-cobaltous oxide was used for lithium ion battery negative material, under 50mA/g～400mA/g charge-discharge velocity test condition, through 50 circulations, its specific storage remained on 900～1300mAh/g.
2. preparation method according to claim 1 is characterized in that: described nano-cobaltic-cobaltous oxide has the porous nanometer structure of one-dimensional chain, and the diameter of porous chain is 60～100nm; Described nano-cobaltic-cobaltous oxide has mesoporous characteristic, and the aperture is 10～20nm.
CN200910019235A 2009-10-13 2009-10-13 Preparation method of nano cobaltosic oxide used for negative electrode material of lithium ion battery Expired - Fee Related CN101928044B (en)

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CN104876284A (en) * 2015-04-17 2015-09-02 济南大学 Nano bead chain cobaltosic oxide and preparation method thereof
CN105645481B (en) * 2016-03-03 2017-10-03 新乡学院 A kind of cobaltosic oxide and preparation method thereof
CN109378453A (en) * 2018-09-25 2019-02-22 齐鲁工业大学 A kind of cobaltosic oxide lithium ion battery negative material of the high circulation performance of nanoscale core-shell structure
CN110316768A (en) * 2019-08-14 2019-10-11 中国科学院青海盐湖研究所 A kind of spinel structure cobalt/cobalt oxide, preparation method and application
CN111551571B (en) * 2020-05-11 2021-02-12 上海大学 Verification method for enhancing lithium storage performance of Fe-Mo bimetal oxide

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1837066A (en) * 2006-04-13 2006-09-27 上海交通大学 Process for temperature-control pressure-control microwave synthesis of water soluble cobaltosic oxide nano crystal
CN101508470A (en) * 2009-03-27 2009-08-19 安徽师范大学 Process for producing stephanoporate one-dimensional nano-cobaltic-cobaltous oxide

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1837066A (en) * 2006-04-13 2006-09-27 上海交通大学 Process for temperature-control pressure-control microwave synthesis of water soluble cobaltosic oxide nano crystal
CN101508470A (en) * 2009-03-27 2009-08-19 安徽师范大学 Process for producing stephanoporate one-dimensional nano-cobaltic-cobaltous oxide

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Yunshuang Ding et al..Syntheses of Nanostructures of Cobalt Hydrotalcite Like Compounds and Co3O4 via a Microwave-Assisted Reflux Method.《J. Phys. Chem. C》.2008,第112卷(第22期),8177–8183. *
袁鹏等.微波均相沉淀法合成纳米粉体的研究进展.《中国粉体技术》.2008,第14卷(第2期),50-53. *

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