CN103746092A - Preparation method of calcium-cobalt oxide compound as anode material for lithium ion batteries - Google Patents

Preparation method of calcium-cobalt oxide compound as anode material for lithium ion batteries Download PDF

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Publication number
CN103746092A
CN103746092A CN201310707150.1A CN201310707150A CN103746092A CN 103746092 A CN103746092 A CN 103746092A CN 201310707150 A CN201310707150 A CN 201310707150A CN 103746092 A CN103746092 A CN 103746092A
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chelate
lithium ion
coo
reactant
sintering
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梁孜
李明科
王睿
郑威
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Dongfang Electric Corp
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Dongfang Electric Corp
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1391Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M2004/026Electrodes composed of or comprising active material characterised by the polarity
    • H01M2004/028Positive electrodes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a preparation method of a lamellar calcium-cobalt oxide compound as an anode material for lithium ion batteries. The method comprises the steps of dissolving reactants including Ca(CH3COO)2, Co(CH3COO)2 and a chelate to prepare a mixed solution, stirring the mixed solution till the mixed solution is in a sol state, drying the sol to obtain xerogel, and then grinding and sintering the xerogel to obtain a finished product Ca3Co4O9. The prepared material is uniform in grains, has high specific capacity and has good charge and discharge efficiency.

Description

A kind of preparation method of lithium ion battery anode material calcium cobalt oxide
Technical field
The present invention relates to a kind of lithium ion battery anode material and preparation method thereof, particularly a kind of preparation method of lithium ion battery anode material calcium cobalt oxygen lamellar compound.
Background technology
Along with mankind's science and technology is growing, to the consumption of the energy and rely on increasing, also more and more heavier to the destruction of environment.The storage of the energy is making full use of earth resource with transforming, and improves the aspects such as human ecological environment and play a part more and more important.Chemical power source, as a kind of important way of energy storage and conversion, is widely used in mankind's daily life.Lithium ion battery relies on the advantages such as energy density is high, life-span length, memory-less effect, in electric automobile, stored energy application, mancarried electronic aid, occupies critical role.
Along with the increasing of lithium ion battery demand, people also more and more pay attention to the research of lithium ion battery material.All the time, graphite is all used as the anode material of lithium ion battery first-selection, but due to the restriction (about 372mAh/g) of its theoretical capacity, people are also seeking other alternative always, study novel lithium ion battery anode material.Recent years, transition metal oxide (cobalt, nickel, copper, iron etc.) has been in the news out and can have realized very large reversible capacity by ion exchange, but capacity attenuation is too fast in actual use, have a greatly reduced quality useful life, and a possible reason is that this class material change in volume in the de-embedding process of lithium ion is excessive.And the complex layered compound that is normally used for thermoelectric material that some are comprised of transition metal oxide, for example Ca 3co 4o 9, this materials chemistry structure is CoO 2with CoCa 2o 3composite stack structure, its structure just in time makes up the structural deficiency of simple transition metal oxide, can effectively suppress the change in volume of transition metal oxide, and possess the feature that thermal stability is high, oxidative resistance is high and toxicity is lower, be a kind of desirable lithium ion battery anode material.The Ca of domestic current preparation 3co 4o 9material is all used in thermoelectric material field, the Ca that the present invention is prepared 3co 4o 9material can be used as lithium ion battery anode material, and possesses good efficiency for charge-discharge.
Separately there is China Patent No. to be: CN201210112609.9 discloses a kind of Ca of special appearance 3co 4o 9/ Ag composite ceramics thermoelectric material preparation method, said method belongs to ceramic thermoelectric Material Field, and it uses inorganic calcium salt and cobalt salt as reactant, at Ca 3co 4o 9in generative process or residual inorganic compound, lithium ion battery material is had to adverse effect.
Summary of the invention
In order to overcome the defect of above-mentioned prior art, the invention provides a kind of preparation method of lithium ion battery anode material calcium cobalt oxygen lamellar compound, this method adopts sol-gal process, and obtained material granule is even, material specific capacity is high, and has good efficiency for charge-discharge.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is:
A preparation method for lithium ion battery anode material calcium cobalt oxygen lamellar compound, is characterized in that: comprise following preparation process:
A, weighing reactant: described reactant comprises Ca (CH 3cOO) 2, Co (CH 3cOO) 2and chelate, described Ca (CH 3cOO) 2with Co (CH 3cOO) 2a mole metering ratio by Ca:Co=3:4 takes; Described chelate is by reacting metal Ca and Co: a mole metering ratio for chelate=1:1~3 takes;
B, dissolving: the reactant in above-mentioned A step is inserted in reaction vessel, be dissolved in the ratio of 0.5~2L deionized water in every moore reactant, solubilizing reaction thing becomes mixed solution;
C, stirring: mixed solution is stirred to collosol state, and whipping temp is controlled at 60 ℃~100 ℃, and mixing time is 3~6h; Then the colloidal sol after stirring is placed in to 100 ℃ of baking oven inner drying 8~16h, obtains xerogel;
D, sintering: xerogel is pulverized, be placed in high temperature furnace sintering, first at 350 ℃~450 ℃ scope pre-burning 16~24h, be then warming up to 600 ℃~700 ℃ sintering 3~6h, obtain Ca 3co 4o 9finished product.
Chelate described in steps A is a kind of in citric acid, tartaric acid, gluconic acid, ethylenediamine tetra-acetic acid.
This materials chemistry formula is Ca 3co 4o 9; This material first discharge specific capacity under 1C multiplying power can reach 1200mAh/g, and after initial charge, material and lithium ion react, and obtains rock-steady structure, and after lower 50 circulations of 1C multiplying power, specific capacity still can reach 400mAh/g.It discharges and recharges reaction:
Ca 3co 4o 9+ 12Li → 3CaO+4Co+6Li 2o (electric discharge first)
4Co+6Li 2o → 1/3[4 (Co 3o 4+ 8Li)+2Li 2o] (initial charge)
4/3 (Co 3o 4+ 8Li) 4/3 (3Co+4Li 2o) (follow-up circulation)
The present invention has the following advantages:
1, this method adopts organic calcium salt and cobalt salt, and organic chelate is as reactant, and after high temperature sintering, organic substance can be removed by reaction completely, gained Ca 3co 4o 9material is applicable to lithium ion battery anode material, obtained Ca 3co 4o 9material purity is higher.
2, the present invention adopts sol-gal process, and raw material mixes enough even, sintering after drying, and gained Ca3Co4O9 material granule size is tiny and even, is conducive to lithium ion and takes off embedding.
3, the obtained Ca of the present invention 3co 4o 9after material repeatedly discharges and recharges, material structure is stable, and cycle performance excellence and specific capacity are high.
Accompanying drawing explanation
Fig. 1 is charging and discharging curve first.
Fig. 2 is the circulation cyclic curve that after 50 weeks, Capacitance reserve is 385mAh/g.
Embodiment
Embodiment 1
Take respectively 0.75mol Ca (CH 3cOO) 2with 1mol Co (CH 3cOO) 2, take chelate citric acid 2mol, previous reaction slaine and chelate are inserted in reaction vessel, add 4L deionized water dissolving reactant.Mixed solution is stirred to collosol state under stirring, and whipping temp is controlled at 80 ℃, and mixing time is 5h; Stirring finishes rear colloidal sol and is placed in 100 ℃ of baking oven inner drying 10h, obtains xerogel.Xerogel is pulverized, be placed in high temperature furnace sintering.First, at 400 ℃ of scope pre-burning 24h, be then warming up to 600 ℃ of sintering 4.5h, obtain Ca 3co 4o 9finished product.
By the Ca making 3co 4o 9finished product mixes in the ratio of 70:20:10 with conductive agent SuperP carbon black, binding agent PVDF, adds organic solvent 1-methyl-2 pyrrolidones (NMP) to stir as solvent.After using homogenizer to stir, be coated on aluminium foil surface, in 80 ℃ of drying boxes, dry, then use tablet press machine compacting evenly, make mesuring battary pole piece.Electrode slice being assembled into coin shape test battery in the glove box of oxygen content≤0.1ppm, water content≤0.1ppm, is wherein metal lithium sheet to electrode, and barrier film is Celgard 2325 composite membranes, and electrolyte is 1 mol/L LiPF 6equal-volume than ethylene carbonate (EC), dimethyl carbonic ether (DMC) solution.The battery that the positive electrode of example 1 preparation fills is done constant current charge-discharge test between 3~0.01V voltage range, under 0.1C (1C=500mA/g) multiplying power, its first discharge capacity be 1153mAh/g.First charge-discharge curve as shown in Figure 1.
Embodiment 2
Take respectively 0.375mol Ca (CH 3cOO) 2with 0.5mol Co (CH 3cOO) 2, take chelate tartaric acid 1mol, reacting metal salt and chelate are inserted in reaction vessel, add 1.5L deionized water dissolving reactant.Mixed solution is stirred to collosol state under stirring, and whipping temp is controlled at 90 ℃, and mixing time is 6h; Stirring finishes rear colloidal sol and is placed in 100 ℃ of baking oven inner drying 14h, obtains xerogel.Xerogel is pulverized, be placed in high temperature furnace sintering.First, at 450 ℃ of scope pre-burning 16h, be then warming up to 700 ℃ of sintering 3h, obtain Ca 3co 4o 9finished product.
By the Ca making 3co 4o 9finished product mixes in the ratio of 70:20:10 with conductive agent SuperP carbon black, binding agent PVDF, adds organic solvent 1-methyl-2 pyrrolidones (NMP) to stir as solvent.After using homogenizer to stir, be coated on aluminium foil surface, in 80 ℃ of drying boxes, dry, then use tablet press machine compacting evenly, make mesuring battary pole piece.Electrode slice being assembled into coin shape test battery in the glove box of oxygen content≤0.1ppm, water content≤0.1ppm, is wherein metal lithium sheet to electrode, and barrier film is Celgard 2325 composite membranes, and electrolyte is 1 mol/L LiPF 6equal-volume than ethylene carbonate (EC), dimethyl carbonic ether (DMC) solution.The battery that the positive electrode of example 2 preparation fills is done constant current charge-discharge test between 3~0.01V voltage range, under 1C (1C=500mA/g) multiplying power, its first discharge capacity be 1162mAh/g.
Embodiment 3
Take respectively 0.375mol Ca (CH 3cOO) 2with 0.5mol Co (CH 3cOO) 2, take chelate gluconic acid 3mol, reacting metal salt and chelate are inserted in reaction vessel, add 8L deionized water dissolving reactant.Mixed solution is stirred to collosol state under stirring, and whipping temp is controlled at 60 ℃, and mixing time is 6h; Stirring finishes rear colloidal sol and is placed in 100 ℃ of baking oven inner drying 16h, obtains xerogel.Xerogel is pulverized, be placed in high temperature furnace sintering.First, at 350 ℃ of scope pre-burning 24h, be then warming up to 650 ℃ of sintering 6h, obtain Ca 3co 4o 9finished product.
By the Ca making 3co 4o 9finished product mixes in the ratio of 70:20:10 with conductive agent SuperP carbon black, binding agent PVDF, adds organic solvent 1-methyl-2 pyrrolidones (NMP) to stir as solvent.After using homogenizer to stir, be coated on aluminium foil surface, in 80 ℃ of drying boxes, dry, then use tablet press machine compacting evenly, make mesuring battary pole piece.Electrode slice being assembled into coin shape test battery in the glove box of oxygen content≤0.1ppm, water content≤0.1ppm, is wherein metal lithium sheet to electrode, and barrier film is Celgard 2325 composite membranes, and electrolyte is 1 mol/L LiPF 6equal-volume than ethylene carbonate (EC), dimethyl carbonic ether (DMC) solution.The battery that the positive electrode of example 3 preparation fills is done constant current charge-discharge test between 3~0.01V voltage range, under 1C (1C=500mA/g) multiplying power, its first discharge capacity be 1139mAh/g.
Embodiment 4
Take respectively 0.75mol Ca (CH 3cOO) 2with 1mol Co (CH 3cOO) 2, take chelate ethylenediamine tetra-acetic acid 4mol, reacting metal salt and chelate are inserted in reaction vessel, add 9L deionized water dissolving reactant.Mixed solution is stirred to collosol state under stirring, and whipping temp is controlled at 100 ℃, and mixing time is 3h; Stirring finishes rear colloidal sol and is placed in 100 ℃ of baking oven inner drying 8h, obtains xerogel.Xerogel is pulverized, be placed in high temperature furnace sintering.First, at 400 ℃ of scope pre-burning 18h, be then warming up to 600 ℃ of sintering 5h, obtain Ca 3co 4o 9finished product.
By the Ca making 3co 4o 9finished product mixes in the ratio of 70:20:10 with conductive agent SuperP carbon black, binding agent PVDF, adds organic solvent 1-methyl-2 pyrrolidones (NMP) to stir as solvent.After using homogenizer to stir, be coated on aluminium foil surface, in 80 ℃ of drying boxes, dry, then use tablet press machine compacting evenly, make mesuring battary pole piece.Electrode slice being assembled into coin shape test battery in the glove box of oxygen content≤0.1ppm, water content≤0.1ppm, is wherein metal lithium sheet to electrode, and barrier film is Celgard 2325 composite membranes, and electrolyte is 1 mol/L LiPF 6equal-volume than ethylene carbonate (EC), dimethyl carbonic ether (DMC) solution.The battery that the positive electrode of example 4 preparations fills is done constant current charge-discharge test between 3~0.01V voltage range, under 0.1C (1C=500mA/g) multiplying power, its first discharge capacity be 1179mAh/g, the Capacitance reserve after 50 weeks that circulates is 385mAh/g, its cyclic curve as shown in Figure 2.

Claims (2)

1. a preparation method for lithium ion battery anode material calcium cobalt oxygen lamellar compound, is characterized in that: comprise following preparation process:
A, weighing reactant: described reactant comprises Ca (CH 3cOO) 2, Co (CH 3cOO) 2and chelate, described Ca (CH 3cOO) 2with Co (CH 3cOO) 2a mole metering ratio by Ca:Co=3:4 takes; Described chelate is by reacting metal Ca and Co: a mole metering ratio for chelate=1:1~3 takes;
B, dissolving: the reactant in above-mentioned A step is inserted in reaction vessel, be dissolved in the ratio of 0.5~2L deionized water in every moore reactant, solubilizing reaction thing becomes mixed solution;
C, stirring: mixed solution is stirred to collosol state, and whipping temp is controlled at 60 ℃~100 ℃, and mixing time is 3~6h; Then the colloidal sol after stirring is placed in to 100 ℃ of baking oven inner drying 8~16h, obtains xerogel;
D, sintering: xerogel is pulverized, be placed in high temperature furnace sintering, first at 350 ℃~450 ℃ scope pre-burning 16~24h, be then warming up to 600 ℃~700 ℃ sintering 3~6h, obtain Ca 3co 4o 9finished product.
2. the preparation method of lithium ion battery anode material calcium cobalt oxygen lamellar compound according to claim 1, is characterized in that: chelate described in steps A is a kind of in citric acid, tartaric acid, gluconic acid, ethylenediamine tetra-acetic acid.
CN201310707150.1A 2013-12-20 2013-12-20 Preparation method of calcium-cobalt oxide compound as anode material for lithium ion batteries Pending CN103746092A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105810936A (en) * 2016-01-11 2016-07-27 湖北大学 Layered structured negative electrode material Ca9Co12O28 of lithium ion battery and preparation method of layered structure negative electrode material
CN110128137A (en) * 2019-05-27 2019-08-16 太原师范学院 A kind of light sensitive ceramics dielectric material and preparation method thereof
CN110600723A (en) * 2019-08-06 2019-12-20 广东工业大学 Ca3Co4O9Nano hollow tube cathode material, sodium ion battery and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101045561A (en) * 2007-04-29 2007-10-03 哈尔滨工业大学 Preparation method of CasCo409 delta prepowder
KR20090006895A (en) * 2007-07-11 2009-01-16 한국과학기술연구원 New calcium-cobalt oxide anode materials and method for manufacturing the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101045561A (en) * 2007-04-29 2007-10-03 哈尔滨工业大学 Preparation method of CasCo409 delta prepowder
KR20090006895A (en) * 2007-07-11 2009-01-16 한국과학기술연구원 New calcium-cobalt oxide anode materials and method for manufacturing the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
陈赛珊等: "EDTA络合溶胶-凝胶法制备Ca3Co4O9粉体", 《材料开发与应用》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105810936A (en) * 2016-01-11 2016-07-27 湖北大学 Layered structured negative electrode material Ca9Co12O28 of lithium ion battery and preparation method of layered structure negative electrode material
CN105810936B (en) * 2016-01-11 2018-07-17 湖北大学 The lithium ion battery negative material Ca of layer structure9Co12O28And preparation method thereof
CN110128137A (en) * 2019-05-27 2019-08-16 太原师范学院 A kind of light sensitive ceramics dielectric material and preparation method thereof
CN110600723A (en) * 2019-08-06 2019-12-20 广东工业大学 Ca3Co4O9Nano hollow tube cathode material, sodium ion battery and preparation method and application thereof

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Application publication date: 20140423