CN103872308A - Preparation method of long-life 3V compound lithium manganese oxide - Google Patents

Preparation method of long-life 3V compound lithium manganese oxide Download PDF

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Publication number
CN103872308A
CN103872308A CN201310662123.7A CN201310662123A CN103872308A CN 103872308 A CN103872308 A CN 103872308A CN 201310662123 A CN201310662123 A CN 201310662123A CN 103872308 A CN103872308 A CN 103872308A
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hours
life
preparation
long
temperature
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CN201310662123.7A
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Chinese (zh)
Inventor
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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Priority to CN201310662123.7A priority Critical patent/CN103872308A/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
    • H01M4/36—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • 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 long-life 3V 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 a 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 the 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, quickly cooling to 30 DEG C and grinding to obtain a long-life 3V compound lithium manganese oxide. A specific capacity of the material can be kept at more than 70% of an initial value after the material is completely and deeply charged and discharged for 100 times through a discharging platform under 3V and 1C.

Description

A kind of preparation method of long-life 3V complex lithium Mn oxide
Technical field
The preparation method who the invention discloses a kind of long-life 3V 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, the main low-voltage complex lithium of this battery Mn oxide is 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 cycle life is short, 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 a kind of preparation method of long-life 3V complex lithium Mn oxide, the 3V complex lithium Mn oxide of preparation has the higher number of times that discharges and recharges, and is applied to battery and can improves its cycle life, to meet the development need of electronic product.。
Summary of the invention
The preparation method who the object of the present invention is to provide a kind of long-life 3V complex lithium Mn oxide, its preparation process 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) 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, being heated to 330 DEG C with the speed of 2 DEG C/min of programming rates again keeps 12 hours, rapidly crucible is taken out and puts into 20 DEG C of air, cool to below 30 DEG C;
(5) take out sinter, grind into powder, crosses 100 mesh sieves, obtains long-life 3V lithium manganese oxygen composite oxide.
The advantage of this method is that method is simple, and the lithium manganese oxygen composite oxide discharge platform of preparing is 3V, 1C, and 100% deep charge, electric discharge, circulate after 100 times, and specific capacity still keeps the more than 70% of initial value.Long-life 3V lithium manganese oxygen composite oxide prepared by this method is applied to the cycle life that can fill 3V button lithium battery and will inevitably improve battery.
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 is 6.5 with 3% ammonia neutralization pH value, then repeatedly washs to pH value 6.8 with deionized water, removes by filter water and obtains 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 in the first speed to 260 DEG C with 1 DEG C/min of programming rate with heating of Muffle furnace, keep 10 hours, being heated to 330 DEG C with the speed of 2 DEG C/min of programming rates again keeps 12 hours, then take out in the air that is put into 20 DEG C, reduce the temperature to rapidly 30 DEG C;
(5) take out sinter, grind into powder, crosses 100 mesh sieves, obtains long-life 3V lithium manganese oxygen composite oxide.
Test its cycle performance 1C and be charged to 3.25V, 1C discharges into 2.0V, so circulation, and specific capacity is initial value after 100 times 72%.
Embodiment 2
(1) get 20mol and analyze pure KMnO 4adding 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 in the first speed to 260 DEG C with 1 DEG C/min of programming rate with heating of Muffle furnace, keep 10 hours, being heated to 330 DEG C with the speed of 2 DEG C/min of programming rates again keeps 12 hours, then take out in the air that is put into 20 DEG C, reduce the temperature to rapidly 30 DEG C; ;
(5) take out sinter, grind into powder, crosses 100 mesh sieves, obtains long-life 3V lithium manganese oxygen composite oxide.
Test its cycle performance 1C and be charged to 3.25V, 1C discharges into 2.0V, so circulation, and specific capacity is initial value after 100 times 70%.

Claims (1)

1. a preparation method for long-life 3V complex lithium Mn oxide, is characterized in that: its preparation process is:
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; The class ball-type manganese dioxide of preparation, 120 DEG C ~ 130 DEG C forced air dryings 3 ~ 6 hours, is then cooled to 20 ~ 25 DEG C naturally; 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; 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, be heated to 330 DEG C with the speed of 2 DEG C/min of programming rates again and keep 12 hours, rapidly crucible is taken out and puts into 20 DEG C of air, cool to below 30 DEG C; Take out sinter, grind into powder, crosses 100 mesh sieves, obtains long-life 3V lithium manganese oxygen composite oxide.
CN201310662123.7A 2013-12-06 2013-12-06 Preparation method of long-life 3V compound lithium manganese oxide Pending CN103872308A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105390694A (en) * 2015-11-28 2016-03-09 天津赫维科技有限公司 Preparation method for positive electrode of 3V rechargeable button type lithium manganese dioxide battery
CN113871584A (en) * 2021-08-31 2021-12-31 蜂巢能源科技有限公司 Layered cobalt-free nickel-free lithium-rich cathode material and preparation method thereof

Citations (4)

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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)

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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: "Lithiated 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》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105390694A (en) * 2015-11-28 2016-03-09 天津赫维科技有限公司 Preparation method for positive electrode of 3V rechargeable button type lithium manganese dioxide battery
CN113871584A (en) * 2021-08-31 2021-12-31 蜂巢能源科技有限公司 Layered cobalt-free nickel-free lithium-rich cathode material and preparation method thereof

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Application publication date: 20140618