CN103872309A - Preparation method of similarly-spherical low-voltage compound lithium manganese oxide - Google Patents

Preparation method of similarly-spherical low-voltage compound lithium manganese oxide Download PDF

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Publication number
CN103872309A
CN103872309A CN201310679121.9A CN201310679121A CN103872309A CN 103872309 A CN103872309 A CN 103872309A CN 201310679121 A CN201310679121 A CN 201310679121A CN 103872309 A CN103872309 A CN 103872309A
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hours
preparation
lithium manganese
manganese oxide
temperature
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郝德利
叶丽光
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TIANJIN HEWEI TECHNOLOGY CO LTD
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TIANJIN HEWEI TECHNOLOGY CO LTD
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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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • 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

Abstract

The invention relates to a preparation method of a similarly-spherical low-voltage compound lithium manganese oxide. The preparation method comprises the following steps: adding KMnO4 powder into 1% diluted hydrochloric acid, introducing hot air at the temperature of 70 DEG C and stirring, keeping temperature of liquid at 50-60 DEG C for 3-5 hours, filtering sediment and neutralizing the pH value of the sediment to be 6.5-7.5 by using 3% ammonia water, washing the sediment till the pH value is 6.8-7.2 by using deionized water, filtering, drying and naturally cooling the sediment; mixing manganese dioxide with LiAC.2H2O according to a mass ratio being 4:1 to grind, and then adding acetone to grind; firing a mixture in a muffle furnace; keeping the temperature at 260 DEG C for 10 hours, keeping the temperature at 330 DEG C for 12 hours, naturally cooling and grinding to obtain a similarly-spherical low-voltage compound lithium manganese oxide. A microstructure of the low-voltage compound lithium manganese oxide prepared by the preparation method is similarly spherical; the low-voltage compound lithium manganese oxide has a specific capacity reaching 200mAh/g and a tap density being 1.9g/cm<3>.

Description

The preparation method of one kind spherical low-voltage complex lithium Mn oxide
Technical field
The preparation method who the invention discloses a kind spherical low-voltage complex lithium Mn oxide, belongs to the innovation of chemical energy storage technology.
Background technology
Can fill 3V button lithium battery is the important battery types of a class, is mainly used in electronic circuit board as data accumulating body stand-by power supply, is widely used on the products such as notebook computer, mobile phone, GPS navigation instrument.At present, this battery is mainly using low-voltage complex lithium Mn oxide as positive active material, and lithium-aluminium alloy is as negative electrode active material, and its advantage is that floating charge good electrical property, self discharge are little, but has the shortcomings such as capacity is low, deep discharge ability.The development trends such as the miniaturization of electronic product, non-maintainingization, function are integrated can be filled the capacity of 3V button lithium battery and must not increase volume in the urgent need to improving.The invention provides the preparation method of a kind spherical low-voltage complex lithium Mn oxide, the class spherical low-voltage complex lithium Mn oxide of preparation has higher specific capacity and tap density, be applied to battery and can improve its capacity and do not increase volume, to meet the development need of electronic product simultaneously.
Summary of the invention
The preparation method who the object of the present invention is to provide a kind spherical low-voltage complex lithium Mn oxide, its preparation method is:
(1) get certain mass and analyze pure KMnO 4powder adds in 20 DEG C ~ 25 DEG C 1% watery hydrochloric acid of 16 times of quality, then pass into 70 DEG C of hot-air agitated liquid, give heating liquid simultaneously, keep fluid temperature between 50 ~ 60 DEG C, continue temperature 3 ~ 5 hours, filtering precipitate, with 3% ammonia neutralization pH value be 6.5 ~ 7.5, then repeatedly wash to pH value 6.8 ~ 7.2 with deionized water, remove by filter water and obtain sphere-like manganese dioxide raw material;
(2) the class ball-type manganese dioxide of preparing, 120 DEG C ~ 130 DEG C forced air dryings 3 ~ 6 hours, is then cooled to 20 ~ 25 DEG C naturally;
(3) dried sphere-like manganese dioxide and the pure lithium acetate crystal (LiAC2H of analysis 2o) mix, mass ratio is 4:1, adds mortar to grind 30 minutes, then adds and the acetone of the quality such as mixture, fully grinds 30 ~ 60 minutes;
(4) mixture is put into alumina ceramic crucible and be first heated to 260 DEG C with the speed of 1 DEG C/min of programming rate at Muffle furnace, keep 10 hours, then be heated to 330 DEG C of maintenances 18 hours with the speed of 2 DEG C/min of programming rates, then naturally cool to room temperature;
(5) take out sinter, grind into powder, crosses 100 mesh sieves, obtains the spherical low voltage lithium manganese of class oxygen composite oxide.
The advantage of this method is that method is simple, and the low voltage lithium manganese oxygen composite oxide microstructure of preparing is that class is spherical, sees Fig. 1, and specific capacity reaches 200mAh/g, higher than the level of existing same type of material 180mAh/g; And tap density is 1.9g/cm 3, higher than existing same type of material 1.6g/cm 3level.Therefore the spherical low voltage lithium manganese of the class oxygen composite oxide that, prepared by this method is applied to the capacity that can fill 3V button lithium battery and will inevitably improve battery.
Brief description of the drawings
The spherical low voltage lithium manganese of Fig. 1 class oxygen composite oxide ESEM picture.
Embodiment
Embodiment 1
(1) get 20mol and analyze pure KMnO 4add in 50L 1% watery hydrochloric acid of 20 DEG C, then pass into 70 DEG C of hot-air agitated liquid, give heating liquid simultaneously, keep fluid temperature at 50 DEG C, continue temperature 3 hours, filtering precipitate, with 3% ammonia neutralization pH value be 6.5, then repeatedly with deionized water wash to pH value be 6.8, remove by filter water and obtain sphere-like manganese dioxide raw material;
(2) the class ball-type manganese dioxide of preparing, 120 DEG C of forced air dryings 3 hours, is then cooled to 20 DEG C naturally;
(3) get the dried sphere-like manganese dioxide of 20g and analyze pure acetate dihydrate crystalline lithium with 5g and mix, add mortar to grind 30 minutes, then add 25g acetone, fully grind 30 minutes;
(4) mixture is put into alumina ceramic crucible and be first heated to 260 DEG C with the speed of 1 DEG C/min of programming rate at Muffle furnace, keep 10 hours, then be heated to 330 DEG C of maintenances 18 hours with the speed of 2 DEG C/min of programming rates, then naturally cool to room temperature;
(5) take out sinter, grind into powder, crosses 100 mesh sieves, obtains the spherical low voltage lithium manganese of class oxygen composite oxide.
Testing its specific discharge capacity is 201mAh/g, and tap density is 1.91g/cm 3.
Embodiment 2
(1) get 20mol and analyze pure KMnO 4add in 25 DEG C of 50L 1% watery hydrochloric acid, then pass into 70 DEG C of hot-air agitated liquid, give heating liquid simultaneously, keep fluid temperature at 60 DEG C, continue temperature 5 hours, filtering precipitate is 7.5 with 3% ammonia neutralization pH value, then repeatedly washs to pH value 7.2 with deionized water, removes by filter water obtain sphere-like manganese dioxide raw material with Buchner funnel;
(2) the class ball-type manganese dioxide of preparing, 130 DEG C of forced air dryings 6 hours, is then cooled to 25 DEG C naturally;
(3) get the dried sphere-like manganese dioxide of 20g and analyze pure acetate dihydrate crystalline lithium with 5g and mix, add mortar to grind 30 minutes, then add 25g acetone, fully grind 60 minutes;
(4) mixture is put into alumina ceramic crucible and be first heated to 260 DEG C with the speed of 1 DEG C/min of programming rate at Muffle furnace, keep 10 hours, then be heated to 330 DEG C of maintenances 18 hours with the speed of 2 DEG C/min of programming rates, then naturally cool to room temperature;
(5) take out sinter, grind into powder, crosses 100 mesh sieves, obtains the spherical low voltage lithium manganese of class oxygen composite oxide.
Testing its specific discharge capacity is 202mAh/g, and tap density is 1.92g/cm 3.

Claims (1)

1. the preparation method of a kind spherical low-voltage complex lithium Mn oxide, is characterized in that: preparation method's step is:
(1) get certain mass and analyze pure KMnO 4powder adds in 20 DEG C ~ 25 DEG C 1% watery hydrochloric acid of 16 times of quality, then pass into 70 DEG C of hot-air agitated liquid, give heating liquid simultaneously, keep fluid temperature between 50 ~ 60 DEG C, continue temperature 3 ~ 5 hours, filtering precipitate is 6.5 ~ 7.5 with 3% ammonia neutralization pH value, then repeatedly washs to pH value 6.8 ~ 7.2 with deionized water, removes by filter water and obtains sphere-like manganese dioxide raw material;
(2) sphere-like manganese dioxide of preparing, 120 DEG C ~ 130 DEG C forced air dryings 3 ~ 6 hours, is then cooled to 20 ~ 25 DEG C naturally;
(3) dried sphere-like manganese dioxide and the pure lithium acetate crystal (LiAC2H of analysis 2o) mix, mass ratio is 4:1, adds mortar to grind 30 minutes, then adds and the acetone of the quality such as mixture, fully grinds 30 ~ 60 minutes;
(4) mixture put into alumina ceramic crucible Muffle furnace first with 1 DEG C of programming rate/speed be heated to 260 DEG C, keeps 10 hours, then is heated to 330 DEG C of maintenances 18 hours with the speed of 2 DEG C/min of programming rates, then naturally cool to room temperature; (5) take out sinter, grind into powder, crosses 100 mesh sieves, obtains the spherical low voltage lithium manganese of class oxygen composite oxide.
CN201310679121.9A 2013-12-14 2013-12-14 Preparation method of similarly-spherical low-voltage compound lithium manganese oxide Pending CN103872309A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5985237A (en) * 1996-10-29 1999-11-16 Honjo Chemical Corporation Process for producing lithium manganese oxide suitable for use as cathode material of lithium ion secondary batteries
CN101597086A (en) * 2009-06-26 2009-12-09 海南大学 Method for preparing nano manganese dioxide with different crystal forms in low-temperature acid solution
CN101746829A (en) * 2008-12-15 2010-06-23 山东神工海特电子科技有限公司 Composite MnO for rechargeable lithium manganese battery 2 Preparation method of positive electrode material
CN102856543A (en) * 2012-09-14 2013-01-02 深圳先进技术研究院 Lithium manganate material and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5985237A (en) * 1996-10-29 1999-11-16 Honjo Chemical Corporation Process for producing lithium manganese oxide suitable for use as cathode material of lithium ion secondary batteries
CN101746829A (en) * 2008-12-15 2010-06-23 山东神工海特电子科技有限公司 Composite MnO for rechargeable lithium manganese battery 2 Preparation method of positive electrode material
CN101597086A (en) * 2009-06-26 2009-12-09 海南大学 Method for preparing nano manganese dioxide with different crystal forms in low-temperature acid solution
CN102856543A (en) * 2012-09-14 2013-01-02 深圳先进技术研究院 Lithium manganate material and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
M.YOSHIO ET AL: "Three V or 4V Li-Mn composite as cathode in Li batteries prepared by LiNO3 method as Li source", 《JOURNAL OF POWER SOURCES》 *
MASAKI YOSHIO ET AL: "ithiated manganese dioxide, Li0.33MnO2, as a 3 V cathode for lithium batteries", 《ELECTROCHIMICA ACTA》 *
陈永等: "不同酸溶液中制备纳米结构MnO2单晶", 《金属学报》 *

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Application publication date: 20140618