CN1300868C - Spinel lithium manganate with stable structure for lithium ion cell and manufacturing method thereof - Google Patents

Spinel lithium manganate with stable structure for lithium ion cell and manufacturing method thereof Download PDF

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Publication number
CN1300868C
CN1300868C CNB031178014A CN03117801A CN1300868C CN 1300868 C CN1300868 C CN 1300868C CN B031178014 A CNB031178014 A CN B031178014A CN 03117801 A CN03117801 A CN 03117801A CN 1300868 C CN1300868 C CN 1300868C
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China
Prior art keywords
lithium
lithium ion
ion battery
preparation
lithium manganate
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CNB031178014A
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CN1455466A (en
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杨永平
陈宝荣
何鵾曙
肖扬
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Yunnan Nengtou Huilong Technology Co ltd
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杨永平
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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
    • 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
    • H01M4/1315—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx containing halogen atoms, e.g. LiCoOxFy
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H01M4/13915—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx containing halogen atoms, e.g. LiCoOxFy
    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • 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)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The present invention relates to spinel lithium manganate with a stable structure for a lithium ion battery and the manufacture method thereof. Electrolytic manganese dioxide with 10 to 20 micro of grain sizes, lithium carbonate with 5 to 10 micro of grain sizes and cobalt oxide with 5 to 10 micro of grain sizes are mixed evenly. The spinel lithium manganate with a stable structure for a lithium ion battery is formed by multielement doping and high-temperature solid state sintering. The components of the present invention comprise 70 to 72% of electrolytic manganese dioxide MnO<2> with contents larger than 92%, 15 to 17% of lithium carbonate Li<2>CO<3> with contents larger than 99.9 %, 10 to 20% of cobalt oxide CoO with contents larger than 70% and 1 to 3% of multielement doping body composed of nickel Ni, chromium Cr, iron Fe, manganese Mg, selenium Si and fluorine F.

Description

Lithium ion battery is with the preparation method of constitutionally stable spinel lithium manganate
Technical field
The present invention relates to the battery manufacturing technology, especially a kind of lithium ion battery is with the preparation method of constitutionally stable spinel lithium manganate.
Background technology
Along with lacking day by day of the energy and going from bad to worse of biological environment, electric vehicle replaces the internal combustion engine selection that is inevitable, the world developed country such as the U.S., France, Germany, Japan etc. have all dropped into the development that a large amount of human and material resources, financial resources are engaged in electric motor car.The Chinese government pays much attention to the electric motor car project, just national key scientific ﹠ technological project is classified in the development vehicle technology as during " eight or five ", the enforcement period of the ninth five-year plan is listed in national great scientific and technological industry engineering item, Tenth Five-Year Plan Period electric vehicle industrialization classified as major scientific and technological project by the Ministry of Science and Technology.
Subject matter that electric motor car at present exists such as price, continual mileage, power performance etc. are all closely related with battery technology.Should have following characteristics as the electric vehicle storage battery: 1. high specific energy and volumetric specific energy: 2. have quick charge and large current discharging capability; 3. good cycle life performance; 4. price is low, and working service is convenient; 5. pollution-free, security performance is good.
Lithium ion battery is owing to having the first-selection that high specific energy and good cycle life performance become the electric vehicle power source, but the performance-critical of lithium-ion-power cell depends on its positive electrode.At present, the extensive use and the anode material for lithium-ion batteries of developing research mainly are lithium cobalt oxygen LiCoO 2, lithium nickel oxygen LiNiO 2With lithium manganese oxygen LiMn 2O 4Three kinds, LiCoO 2Operating voltage with good electrochemical and 3.6 volts, technology are comparatively ripe, be the main product in current market, but the reserves of cobalt are limited, cost an arm and a leg, and have certain potential safety hazard, face the trend that is substituted by other products.LiNiO 2Has the advantage on price and the reserves, its actual capacity 190mAh.g -1～210mAh.g -1Near 70～80% of theoretical capacity, but operating voltage is low, the preparation difficulty is big.The LiMn2O4 LiMn of spinel structure 2O 4Has positive electrode characteristic preferably, have cheap, characteristics such as operating voltage is high, self discharge is little, safety non-pollution, cost performance height, it is the first-selected positive electrode of lithium-ion-power cell, but carrying out along with the battery charging and discharging circulation, the phenomenon of capacity attenuation occurs, thereby cause cycle performance poor.
Summary of the invention
Purpose of the present invention just is to overcome above-mentioned the deficiencies in the prior art; the preparation method of a kind of lithium ion battery with constitutionally stable spinel lithium manganate proposed; it is to be raw material with lithium carbonate and electrolytic manganese dioxide; through doping vario-property; mode with multi-element doping; form the high product of capacitance through high temperature solid-phase sintering; it is characterized in that: with the electrolytic manganese dioxide 70～72% of particle diameter 10～20 μ m; the lithium carbonate 15～17% of particle diameter 5～10 μ m; the cobalt oxide 10～20% of particle diameter 5～10 μ m and by nickel; chromium Cr; iron Fe; magnesium Mg; selenium Se; the multi-element doping body 1～3% that fluorine F forms mixes; go in the continous way sintering furnace; heated at constant temperature 12～the 15h under 110～130 ℃ temperature of elder generation; follow heated at constant temperature 18～20h under 550～750 ℃ of temperature; under 800～850 ℃ of temperature, heat 12～15h at last; after roasting has been reacted; natural cooling is 10 hours in the continous way sintering furnace; hierarchical verification promptly obtains product; the content summation of described each component is 100%; this method can effectively be improved the cycle performance of product; the preparation method is simple and easy to control; the technological process of production is short, is fit to large-scale industrial production.
The content of above-mentioned used electrolytic manganese dioxide is greater than 92%; The content of lithium carbonate is greater than 99.9%; The content of cobalt oxide is greater than 70%.
The present invention compared with prior art has following advantage:
1, preparation method's technology of the present invention's proposition is simple and easy to control, has shortened flow process, saves the reaction time, can reduce production costs, increase economic benefit, and can guarantee that synthetic LiMn2O4 is a spinel structure, but and large-scale industrial production, daily output can reach 1100 kilograms.
2, the present invention adopts the mode of multi-element doping in preparation, makes LiMn 2O 4The lattice structure of spinel structure move solid and can form diaphragm on the surface, cobalt, nickel, chromium, iron, magnesium, silicon, the fluorine element that adds is not to enter the octahedra center of spinelle to replace manganese but exist between the spinelle structure cell, play the stable spinel effect, prevent destroyed; These elements are little to spinelle cell space stabilizing influence, and in charge and discharge process, lithium ion can freely be come in and gone out in the spinelle structure cell.
3, the product capacity height of the present invention's acquisition, good cycle, this product is at EC: DMC (1: 1)+1mol/lLiPF 6Show charge-discharge performance and excellent cycle performance preferably in the electrolyte, and product structure is stable, discharge capacity reaches 130mAh.g first -1, 500 circulation back capacity are held rate and can be reached 73.41%.

Claims (4)

1, lithium ion battery is with the preparation method of constitutionally stable spinel lithium manganate, it is characterized in that: with the electrolytic manganese dioxide 70～72% of particle diameter 10～20 μ m, the lithium carbonate 15～17% of particle diameter 5～10 μ m, the cobalt oxide 10～20% of particle diameter 5～10 μ m and by nickel, chromium Cr, iron Fe, magnesium Mg, selenium Se, the multi-element doping body 1～3% that fluorine F forms mixes, go in the continous way sintering furnace, heated at constant temperature 12～the 15h under 110～130 ℃ temperature of elder generation, follow heated at constant temperature 18～20h under 550～750 ℃ of temperature, under 800～850 ℃ of temperature, heat 12～15h at last, after roasting has been reacted, natural cooling is 10 hours in the continous way sintering furnace, hierarchical verification promptly obtains product, and the content summation of described each component is 100%.
2, lithium ion battery is with the preparation method of constitutionally stable spinel lithium manganate according to claim 1, and it is characterized in that: the content of used electrolytic manganese dioxide is greater than 92%.
3, lithium ion battery is with the preparation method of constitutionally stable spinel lithium manganate according to claim 1, and it is characterized in that: the content of used lithium carbonate is greater than 99.9%.
4, lithium ion battery is with the preparation method of constitutionally stable spinel lithium manganate according to claim 1, and it is characterized in that: the content of used cobalt oxide is greater than 70%.
CNB031178014A 2003-04-30 2003-04-30 Spinel lithium manganate with stable structure for lithium ion cell and manufacturing method thereof Expired - Lifetime CN1300868C (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102195042A (en) * 2010-03-09 2011-09-21 中国科学院过程工程研究所 High performance lithium ion battery anode material lithium manganate and preparation method thereof

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101117234B (en) * 2006-08-04 2010-05-12 比亚迪股份有限公司 Method for preparing doping lithium-enriching spinelle lithium manganese oxide
CN101964416B (en) * 2010-10-25 2012-06-27 湖南长远锂科有限公司 Preparation method of lithium ion battery anode material lithium manganate and automobile lithium ion battery
EP2717360B1 (en) 2011-05-23 2017-11-29 Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences Preparing method of a positive electrode material for lithium battery

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999040029A1 (en) * 1998-02-09 1999-08-12 H.C. Starck Gmbh & Co. Kg Method for producing lithium-transition metal mixtures
CN1283313A (en) * 1997-12-22 2001-02-07 石原产业株式会社 Lithium manganate, method of producing the same and lithium cell using the same
CN1380709A (en) * 2001-04-11 2002-11-20 中南大学 Lithium manganate and its preparation method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1283313A (en) * 1997-12-22 2001-02-07 石原产业株式会社 Lithium manganate, method of producing the same and lithium cell using the same
WO1999040029A1 (en) * 1998-02-09 1999-08-12 H.C. Starck Gmbh & Co. Kg Method for producing lithium-transition metal mixtures
CN1380709A (en) * 2001-04-11 2002-11-20 中南大学 Lithium manganate and its preparation method

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102195042A (en) * 2010-03-09 2011-09-21 中国科学院过程工程研究所 High performance lithium ion battery anode material lithium manganate and preparation method thereof

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