CN1328351A - Method for increasing meso-position radius and jolt density of lithium cobaltate - Google Patents

Method for increasing meso-position radius and jolt density of lithium cobaltate Download PDF

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Publication number
CN1328351A
CN1328351A CN01123431A CN01123431A CN1328351A CN 1328351 A CN1328351 A CN 1328351A CN 01123431 A CN01123431 A CN 01123431A CN 01123431 A CN01123431 A CN 01123431A CN 1328351 A CN1328351 A CN 1328351A
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meso
licoo
position radius
tap density
lithium
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CN1147951C (en
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周恒辉
杨正
任献举
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Xianxing Science-Technology-Industry Co., Ltd., Beijing Univ
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Xianxing Science-Technology-Industry Co Ltd Beijing Univ
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

A process for improving the meso-position radius and jolt density of lithium cobaltate includes proportionally mixing Li2CO3, LiOH, or their mixture, CoCO3, Co3O4, or their mixture and LiCoO2, synthesizing at 300-1000 deg.C for 2-20 hr, and breaking the coagulated substance. It can be used for high-energy power supply (Li-ion battery).

Description

A kind of meso-position radius of cobalt acid lithium and method of tap density of improving
Technical field: the invention belongs to the technical field of high capacity power source, especially design a kind of raising cobalt acid lithium (LiCoO 2) meso-position radius and the method for tap density.
Background technology: LiCoO 2As the positive electrode of lithium ion battery, because of its specific capacity height, stable performance and preparation technology are simple to be commercially produced widely.Work as LiCoO 2Meso-position radius D50＜10 micron (μ m) of particle size distribution the time, LiCoO 2Surface activity big and make the fail safe of lithium ion battery relatively poor; And less (＜2.5 gram/cubic centimetre (g/cm of tap density 3)), be difficult to improve the volume and capacity ratio of lithium ion battery.In order to improve the performance of this two aspect, i.e. D50＞10 micron and tap density＞2.5g/cm 3, people often adopt improve the lithium cobalt than (Li/Co) (＞1.00) ratio and temperature (＞900 ℃) or repeatedly method such as sintering realize, as list of references:
1.T.Nakamura，A.Kajiyama，Solid?State?Ionics?123(1999)95～101
2.N.Imanishi，M.Fujii，A.Hirano，et?al.，Solid?State?Ionics?140(2001)45～53
3.Glenn?G?Amatucci，Jean-Marie?Tarascon，US005693435A?Dec.2，1997
But this will cause LiCoO 2Specific capacity and average voltage lower, and the energy consumption of suitability for industrialized production is big.
Summary of the invention: the objective of the invention is under the situation that keeps existing performance,, synthesize the big LiCoO of tap density and meso-position radius as specific discharge capacity＞140mAh/g (Milliampere Hour/gram) 2
Technical scheme of the present invention is:
1. with lithium salts, cobalt salt and LiCoO 2Three kinds of materials mix in proportion; Lithium carbonate (Li 2CO 3), LiOH (lithium hydroxide) or both mixtures, CoCO 3(cobalt carbonate), cobalt oxide (Co 3O 4) or both mixture, LiCoO 2Three kinds of mixing of materials are even;
2. 300～1000 ℃ of following Synthetic 2～20 hour;
3. will synthesize the aggregate fragmentation in the material, obtain LiCoO2 of the present invention.
Lithium salts of the present invention is Li 2CO 3, LiOH or both mixtures, cobalt salt is CoCO 3, Co 3O 4Or both mixtures.The Li/Co ratio of lithium salts and cobalt salt is 0.95～1.10.
The LiCoO that the present invention is used 2The weight ratio that accounts for whole material is for greater than 0% less than 100%, meso-position radius D50＜10 micron and tap density＜2.5g/cm 3
With the prepared LiCoO of said method 2Meso-position radius D50＞10 μ m, tap density＞2.5g/cm 3, specific discharge capacity＞140mAh/g, the LiCoO that other performance is synthetic not second to other method 2The present invention be advantageous in that: with LiCoO 2Be nucleus, cobalt salt and lithium salts are at the formed LiCoO of its surface reaction 2Macroparticle has overcome once-firing LiCoO 2The possible particle internal-response that macroparticle caused is incomplete and crystal formation is imperfect; And avoided to improving LiCoO 2Meso-position radius and tap density and with LiCoO 2The repeatedly excessive volatilization of the lithium that causes of sintering and to the destruction of particle surface, and energy consumption is huge.The LiCoO that adopts the inventive method to make 2Can be used for lithium ion battery.Lithium ion battery is widely used in mobile phone as high capacity power source, notebook computer, gamma camera, electric bicycle and electric automobile etc.
Embodiment: example 1
Li 2CO 3And Co 3O 4The Li/Co ratio be 1.02; LiCoO 2Weight to account for 10%, three kind of mixing of materials of whole material even; Mixed material synthesizes down at 500 ℃, and sintering time is 5 hours; After the cooling with LiCoO 2Broken.LiCoO 2Meso-position radius D50:10.5 μ m, tap density: 2.6g/cm 3, specific discharge capacity: 144mAh/g.Example 2
Li 2CO 3And Co 3O 4The Li/Co ratio be 1.03; LiCoO 2Weight to account for 30%, three kind of mixing of materials of whole material even; Mixed material synthesizes down at 700 ℃, and sintering time is 8 hours; After the cooling with LiCoO 2Broken.LiCoO 2Meso-position radius D50:11.2 μ m, tap density: 2.65g/cm 3, specific discharge capacity: 143mAh/g.Example 3
Li 2CO 3And Co 3O 4The Li/Co ratio be 1.05; LiCoO 2Weight to account for 50%, three kind of mixing of materials of whole material even; Mixed material synthesizes down at 800 ℃, and sintering time is 4 hours; After the cooling with LiCoO 2Broken.LiCoO 2Meso-position radius D50:12.0 μ m, tap density: 2.7g/cm 3, specific discharge capacity: 145mAh/g.Example 4
Li 2CO 3And Co 3O 4With CoCO 3The Li/Co ratio of (weight ratio of two cobalt salts is 8: 2) is 1.O8; LiCoO 2Weight to account for 60%, three kind of mixing of materials of whole material even; Mixed material synthesizes down at 900 ℃, and sintering time is 10 hours; After the cooling with LiCoO 2Broken.LiCoO 2Meso-position radius D50:13.2 μ m, tap density: 2.75g/cm 3, specific discharge capacity: 145mAh/g.Example 5
Li 2CO 3With the weight ratio of LiOH be 3: 7, and Co 3O 4The Li/Co ratio be 1.03; LiCoO 2Weight to account for 90%, three kind of mixing of materials of whole material even; Mixed material synthesizes down at 400 ℃, and sintering time is 15 hours; After the cooling with the LiCoO2 fragmentation.LiCoO 2Meso-position radius D50:11.8 μ m, tap density: 2.55g/cm 3, specific discharge capacity: 142mAh/g.

Claims (6)

1. one kind is improved the meso-position radius of cobalt acid lithium and the method for tap density, and its step comprises
1) with lithium salts, cobalt salt and LiCoO 2Three kinds of mixing of materials are even; Li 2CO 3, LiOH or both mixtures, CoCO 3, Co 3O 4Or both mixtures, LiCoO 2Three kinds of mixing of materials are even;
2) 300～1000 ℃ of following Synthetic 2～20 hour;
3) will synthesize the aggregate fragmentation of back in the material.
2. a kind of meso-position radius of cobalt acid lithium and method of tap density of improving as claimed in claim 1 is characterized in that lithium salts is Li 2CO 3, LiOH or both mixtures.
3. a kind of meso-position radius of cobalt acid lithium and method of tap density of improving as claimed in claim 1 is characterized in that cobalt salt is CoCO 3, Co 3O 4Or both mixtures.
4. a kind of meso-position radius of cobalt acid lithium and method of tap density of improving as claimed in claim 1 is characterized in that LiCoO 2The weight ratio that accounts for whole material for greater than 0% less than 100%.
5. a kind of meso-position radius of cobalt acid lithium and method of tap density of improving as claimed in claim 1, the Li/Co ratio that it is characterized in that lithium salts and cobalt salt is 0.95～1.10.
6. a kind of meso-position radius of cobalt acid lithium and method of tap density of improving as claimed in claim 1 is characterized in that raw materials used LiCoO 2Meso-position radius＜10 micron, tap density＜2.5g/cm 3
CNB011234318A 2001-07-23 2001-07-23 Method for increasing meso-position radius and jolt density of lithium cobaltate Expired - Lifetime CN1147951C (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1420470A3 (en) * 2002-05-30 2004-08-04 Sulzer Hexis AG Process for the preparation of a coating paste
CN100385248C (en) * 2004-06-01 2008-04-30 肇庆市风华锂电池有限公司 Method for testing battery electrode material filling properties
CN102169990A (en) * 2011-04-07 2011-08-31 先进储能材料国家工程研究中心有限责任公司 Ternary cathode material and production method thereof
CN102779976A (en) * 2011-10-10 2012-11-14 北大先行科技产业有限公司 Preparation method of cathode material of LCO (lithium cobaltate)-based lithium ion battery

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1420470A3 (en) * 2002-05-30 2004-08-04 Sulzer Hexis AG Process for the preparation of a coating paste
CN100385248C (en) * 2004-06-01 2008-04-30 肇庆市风华锂电池有限公司 Method for testing battery electrode material filling properties
CN102169990A (en) * 2011-04-07 2011-08-31 先进储能材料国家工程研究中心有限责任公司 Ternary cathode material and production method thereof
CN102169990B (en) * 2011-04-07 2013-06-26 先进储能材料国家工程研究中心有限责任公司 Ternary cathode material and production method thereof
CN102779976A (en) * 2011-10-10 2012-11-14 北大先行科技产业有限公司 Preparation method of cathode material of LCO (lithium cobaltate)-based lithium ion battery
CN102779976B (en) * 2011-10-10 2015-05-20 北大先行泰安科技产业有限公司 Preparation method of cathode material of LCO (lithium cobaltate)-based lithium ion battery

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