CN1357933A - Prepn of LiCoC2 as nanometer positive electrode material for lithium ion cell - Google Patents

Prepn of LiCoC2 as nanometer positive electrode material for lithium ion cell Download PDF

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Publication number
CN1357933A
CN1357933A CN00134039A CN00134039A CN1357933A CN 1357933 A CN1357933 A CN 1357933A CN 00134039 A CN00134039 A CN 00134039A CN 00134039 A CN00134039 A CN 00134039A CN 1357933 A CN1357933 A CN 1357933A
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China
Prior art keywords
cobalt
lithium
compound
raw material
ion cell
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Pending
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CN00134039A
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Chinese (zh)
Inventor
力虎林
申承民
张校刚
周盈科
史彦莉
刘埃林
李云飞
汪英杰
孙曙光
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CHEMISTRY & CHEMICAL ENGINEERING COLLEGE LANZHOU UNIV
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CHEMISTRY & CHEMICAL ENGINEERING COLLEGE LANZHOU UNIV
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Priority to CN00134039A priority Critical patent/CN1357933A/en
Publication of CN1357933A publication Critical patent/CN1357933A/en
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/02—Particle morphology depicted by an image obtained by optical microscopy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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

Abstract

The preparation of LiCoC2 as nanometer positive electrode material for lithium ion cell features that lithium compound and cobelt compound are mixed in the molar ratio of 1.0-1.2, milled in ball mill, roasted in 550-750 deg.C for 10-24 hr and ground to obtain nanometer powder. The LiCoC2 material prepared based on the side process had excellent circulation performance and small particles, 50-200 nm, and the preparation process is simple.

Description

A kind of lithium ion cell nano anode material LiCoO 2The preparation method
The present invention relates to lithium ion cell nano anode material LiCoO 2The preparation method of powder.
At present, Jue Daduoshuo battery production producer mainly uses LiCoO 2As positive electrode.LiCoO 2Belong to a stratiform compound, with Li xNiO 2And Li 1+xMnO 2Compare, have stable structure, high discharge platform and energy density and cyclical stability.
Traditional LiCoO 2The preparation method adopts high temperature sintering production.Thomas, people such as M.G.S.R. [J.Electrochem.Soc., 132 (1985), 1521-1528] grind with proper proportion with lithium carbonate and cobalt carbonate (or cobalt oxide),, form in 24 hours at high temperature sintering more than 900 ℃ after 12 hours 600 ℃ of burnings again.This method prepares the chemical property instability of sample, and battery capacity is not high, and after its main cause was high temperature sintering, lithium can lose, and causes metering than changing; Tang causes the people's of grade far away application for a patent for invention (publication number is CN241823A), prepares LiCoO by two-step synthetic method 2This method is because employing divides one-step baking, and under certain pressure, compacting is in blocks, and technology is complicated.The material that above-mentioned these methods are synthetic, particle size be big (several to tens μ m), and specific area is little, causes the material loose contact sometimes.
The objective of the invention is to improve shortcoming of the prior art, adopt simply and easily synthesis technique to prepare nanometer LiCoO with height ratio capacity and excellent cycle performance 2Powder.
Main technical schemes of the present invention: with lithium compound and cobalt compound mixed in molar ratio, use ball mill grinding,, promptly obtain LiCoO at 550-750 ℃ of roasting temperature with certain metering 2Superfine powder.
Preparation method of the present invention may further comprise the steps:
A kind of lithium ion cell nano anode material LiCoO 2The preparation method of powder is characterized in that preparation process comprises:
(1) with lithium compound and cobalt compound raw material with 1.0-1.2: 1 mixed in molar ratio, mix in grinding machine for grinding then,
(2) raw material that mixes of step (1) at 550-750 ℃ roasting temperature 10-20 hour, is cooled to room temperature,
(3) with the sample that cools off after step (2) roasting in grinding in ball grinder, promptly obtain the nano powder product.
When raw material lithium compound that the present invention is used and cobalt compound did not contain the crystallization water, step (1) need add certain quantity of additive when grinding, and purpose is to improve its reaction speed and reactant is mixed; Described additive is an industrial alcohol, and its addition is the 5-10% of lithium compound and cobalt compound raw material weight; If containing the crystallization water, lithium compound and cobalt compound can directly grind.
The used lithiumation thing of the present invention is lithium hydroxide or lithium nitrate.
The used cobalt compounds of the present invention is selected from any in anhydrous nitric acid cobalt, cobalt nitrate hexahydrate, acetic anhydride cobalt, Cobalt diacetate tetrahydrate, cobalt oxalate and the cobalt hydroxide.
Grinder of the present invention is known mechanical grinding device, and the baking furnace patent applied for that described roasting is used, number of patent application are 00263253.5.
Major advantage of the present invention:
The present invention is owing to adopt the one-step method roasting to make required product, therefore technology is simple, and required equipment is few, production cost is relatively low, product particle by method preparation of the present invention is of a size of 50-200mm, be used for battery and have higher specific capacity and good cycle performance, cycle-index is more than 500 times.
Further specify characteristics of the present invention below by concrete example.
Example 1
With lithium hydroxide and cobalt nitrate hexahydrate by mixed with 1.1: 1 mole, place agate mortar, grind equably, in 560 ℃ roasting temperatures 19 hours, take out after being cooled to room temperature, grind to form powdery, its XRD (X-ray diffraction) and TEM (transmission electron microscope) the results are shown in Figure 1, Fig. 2.
Example 2
Replace cobalt nitrate hexahydrate in the example 1 with Cobalt diacetate tetrahydrate, its mol ratio is 1.2: 1,740 ℃ of sintering temperatures, and 12 hours time, other preparation condition is consistent with example 1, the results are shown in Figure 3 and Fig. 4.
Example 3
Lithium hydroxide and anhydrous nitric acid cobalt by the mixed with 1.1: 1 mole, are placed agate mortar, add 6% industrial alcohol of example weight, grind equably,, take out after being cooled to room temperature, grind to form powdery in 600 ℃ roasting temperatures 16 hours.Its XRD (X-ray diffraction) and TEM (transmission electron microscope) result and example 1 basically identical.
Example 4
Lithium hydroxide and acetic anhydride cobalt are mixed by the molar ratio with 1: 1, place agate mortar, adding additive industrial alcohol (example weight 10%), grind equably, in 750 ℃ roasting temperatures 10 hours, take out after being cooled to room temperature, grind to form powdery.Its XRD (X-ray diffraction) and TEM (transmission electron microscope) result and enforcement 2 basically identicals.

Claims (4)

1. lithium ion cell nano anode material LiCoO 2The preparation method of powder is characterized in that preparation process comprises:
(1) with lithium compound and cobalt compound raw material with 1.0-1.2: 1 mixed in molar ratio, mix in grinding machine for grinding then,
(2) raw material that mixes of step (1) at 550-750 ℃ roasting temperature 10-20 hour, is cooled to room temperature,
(3) with the sample that cools off after step (2) roasting in grinding in ball grinder, promptly obtain the nano powder product.
2. according to the described method of claim 1, it is characterized in that the described lithium compound of step (1) is lithium hydroxide or lithium nitrate.
3. method according to claim 1 is characterized in that described cobalt compound is selected from any in anhydrous nitric acid cobalt, cobalt nitrate hexahydrate, acetic anhydride cobalt, Cobalt diacetate tetrahydrate, cobalt oxalate and the cobalt hydroxide.
4. method according to claim 1 is characterized in that step (1) process of lapping need add additive when lithium compound and cobalt compound raw material do not contain the crystallization water, and described additive is that industrial wine is clear, and its addition is the 5-10% of raw material weight.
CN00134039A 2000-12-08 2000-12-08 Prepn of LiCoC2 as nanometer positive electrode material for lithium ion cell Pending CN1357933A (en)

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CN00134039A CN1357933A (en) 2000-12-08 2000-12-08 Prepn of LiCoC2 as nanometer positive electrode material for lithium ion cell

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102779974A (en) * 2011-05-09 2012-11-14 凌春喜 Nanometer cell and manufacturing method for processing of same
CN103151517A (en) * 2013-01-23 2013-06-12 宁波维科电池股份有限公司 Preparation method of lithium cobalt oxide
CN103466665A (en) * 2006-02-28 2013-12-25 普里梅精密材料有限公司 Lithium-based compound nanoparticle compositions and methods of forming the same
CN113526565A (en) * 2021-07-09 2021-10-22 天津大学 Method for rapidly synthesizing lithium cobaltate cathode material and application

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103466665A (en) * 2006-02-28 2013-12-25 普里梅精密材料有限公司 Lithium-based compound nanoparticle compositions and methods of forming the same
CN102779974A (en) * 2011-05-09 2012-11-14 凌春喜 Nanometer cell and manufacturing method for processing of same
CN102779974B (en) * 2011-05-09 2015-09-30 凌春喜 Nano cell and process this nano cell manufacture method
CN103151517A (en) * 2013-01-23 2013-06-12 宁波维科电池股份有限公司 Preparation method of lithium cobalt oxide
CN103151517B (en) * 2013-01-23 2015-04-22 宁波维科电池股份有限公司 Preparation method of lithium cobalt oxide
CN113526565A (en) * 2021-07-09 2021-10-22 天津大学 Method for rapidly synthesizing lithium cobaltate cathode material and application

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