CN1326232A - Process for preparing lithium manganese oxide as positive electrode of lithium ion battery - Google Patents

Process for preparing lithium manganese oxide as positive electrode of lithium ion battery Download PDF

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Publication number
CN1326232A
CN1326232A CN00112964A CN00112964A CN1326232A CN 1326232 A CN1326232 A CN 1326232A CN 00112964 A CN00112964 A CN 00112964A CN 00112964 A CN00112964 A CN 00112964A CN 1326232 A CN1326232 A CN 1326232A
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positive electrode
organic acid
acid
roasting
manganese
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于作龙
刘培松
高利珍
李庆
张伯兰
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Chengdu Institute of Organic Chemistry of CAS
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Chengdu Institute of Organic Chemistry of CAS
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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
    • 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
    • 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
    • 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)
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  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

A process for preparing Li-Mn oxide material as positive of lithium ion battery, which is also suitable for synthesizing the composite oxide material with spinal structure, uses Li salt and Mn source (MnO2 and metal manganese) as raw materials and includes such steps as adding organic acid (acetic acid and/or etharedioic acid and/or oxalic acid and/or citric acid), evaporating solvent to obtain gel precursor, drying and calcining.

Description

A kind of preparation method of lithium manganese oxide as positive electrode of lithium ion battery
The present invention relates to a kind of preparation method of lithium manganese oxide as positive electrode of lithium ion battery, be applicable to have the synthetic of spinel structure composite oxide material simultaneously.
LiCoO 2Positive electrode is applied in " rocking chair " formula lithium ion battery of its exploitation by Sony Corporation at first, and it has advantages such as normal electrode voltage height, discharge is steady, the temperature scope of application is wide.But Co has pollution to environment, LixCoO during actual the use 2Lithium ion can not take off embedding fully and make shortcomings such as the capacity of negative material is restricted in (0.5＜x＜1).With LiCoO 2Compare LiNiO 2Low price some, have preferably high-temperature stability, self-discharge rate low, with electrolyte good compatibility is arranged, but the preparation of material and purge process difficulty comparatively.Lithium manganese oxide is the most popular positive electrode of research at present.Standard electrode potential height (4V vsLi +/ Li), and aboundresources, environmental pollution is few.Take all factors into consideration factors such as performance and cost and environment, LiMn 2O 4Compare with other two kinds of materials and to have comparatively remarkable advantages, use lithium manganese oxide to substitute LiCoO 2It is one of researcher's direction of making great efforts always.
The application of lithium ion battery in electric motor car and hybrid (hybrid) electric motor car launches.At present, use as electric motor car, cost is a deciding factor.Co system and Ni are that battery is on a sticky wicket in this respect.When battery maximized, Co system and Ni were the problem that there is fail safe in battery in addition, and Mn is that application is competitive to battery as electric motor car.Germany's Wa Erta Battery Company (Varta BatteriesA G) is thought LiMn 2O 4Positive electrode can be made high-energy and high power type electric vehicle battery.The 60Ah battery had been made by the said firm in 1997, and when specific power was 30KW/Kg, specific energy was 115Wh/Kg.As the civilian traffic electric motor car of practical application, be that the lithium ion battery of positive electrode is the most potential candidate of realizing this goal with the lithium manganese oxide.
Solid phase method is the most frequently used synthetic method of lithium manganese oxide material, but has long, shortcoming such as energy consumption is high, granularity is inhomogeneous of reaction time.Because solid phase reaction at first depends on the diffusion between the material, contact by mechanical batch mixing physics between the different component, reaction temperature of generally having relatively high expectations and long reaction time, the preparation product exists at aspects such as composition, structure, particle size distribution than big difference, therefore causes material electrochemical performance wayward.
In order to overcome the defective of high temperature solid state reaction, adopt the Pechini method can be good at the synthetic crystalline structure of lower temperature, the material of granule size and distribution uniform.It forms complex compound by metal ion and citric acid, and esterification formation high polymer evenly mixes raw material then.Reduce the diffusional resistance in the solid phase reaction like this, thereby reduced sintering temperature, shortened the reaction time.But in the material preparation process, because initiation material cost height, the preparation process complexity is difficult to adapt to industrial production requirement.
Employing alcohol-water mixtures such as Yoshida (EP 0816292 A1) prepare the lithium manganese oxide material as decentralized medium, and the gellike mixture that forms in the whipping process is distributed in the hole of porous manganese dioxide lithium salts.Because methyl alcohol mainly plays peptizaiton, can't react with manganese dioxide, consider simultaneously that methyl alcohol is inflammable in process of production, environment had shortcoming such as pollution will limit its use.
Consider above situation, the object of the invention provides a kind of simple, easy industrialized material preparation method.Principle of the present invention be achieved in that organic acid can with water-fast Mn salt generation chemical reactions such as electrolytic manganese dioxide (EMD), chemical manganese bioxide (CMD) or manganese carbonate, also can dissolve water-fast lithium carbonate or the lower lithium hydroxide of solubility in the Li salt, therefore increased the contact area between Li, the Mn, organic acid plays the effect of reactant and decentralized medium simultaneously.The presoma that obtains is in roasting process, generation gas takes place to decompose in organic acid, it is more even to obtain material granule, the carbon part that organic acid decomposition simultaneously produces penetrates in the material structure and goes, can increase the electron conduction between the lithium manganese oxide particles, reduce the internal resistance of cell, polarization phenomena take place when reducing battery charge, improve the material cycle performance.
Here narrate the preparation of lithium manganese oxide material of the present invention.
In organic acid solution, add Mn compound high-speed stirred, Mn salt is dispersed in the organic acid solution, under constantly stirring, add the Li compound.Perhaps in organic acid soln, add Li salt high-speed stirred, add the Mn compound then.Evaporation removes and desolvates, and oven dry obtains presoma in 100 ℃ baking oven.Presoma at 400 ℃ of predecomposition 1-6h, is warmed up to 700-800 ℃ of roasting 8-16h, natural cooling.
Be a kind of Li compound, Mn compound to be mixed in organic acid soln below, and the method for optimizing that the compound that is obtained is carried out roasting.
In the compound of Li salt and Mn salt, the organic acid of molal quantitys such as adding and Li, Mn.The solution high-speed stirred is evenly disperseed Li salt, Mn salt and decentralized medium.Dispersion effect is better when organic acid is acetate, ethanedioic acid, citric acid, oxalic acid.Slowly transpiring moisture obtains gel.Obtain presoma 105 ℃ of oven dry then.With 400 ℃ of predecomposition 2h of presoma, 0.5～5 ℃/min of control programming rate is warming up to 700-800 ℃, cooling naturally behind the roasting 10-14h.The material and the lithium sheet that are obtained are formed simulated battery, find that this material has than high discharge capacity.
Above-mentioned presoma heats in air atmosphere, heats better in flow air atmosphere, and preferably heats in oxygen flow.
In order better to set forth the present invention, be elaborated below in conjunction with embodiment and accompanying drawing.
Embodiment 1
With EMD is the Mn source, and LiOH is the Li source, and citric acid is done reaction medium.2.5g LiOH and 10.5gEMD are joined in the deionized water, be mixed into suspension, then the citric acid of molal quantitys such as adding and manganese dioxide.Solution obtains starching attitude thickness mud thing at 80 ℃ of transpiring moistures, and 100 ℃ of vacuumizes obtain loose block presoma.Presoma at 400 ℃ of predecomposition 2h, is risen to natural cooling behind 750 ℃ of constant temperature 10h with the programming rate of 1 ℃/min.The XRD figure that obtains material is seen Fig. 1.This material is spinel structure (Fd3m), does not observe other impurity peaks.Find out that from the stereoscan photograph (Fig. 2) of material granular size is more even.With this material and acetylene black, polytetrafluoroethylene is 85: 10: 5 mixed by weight, is coated on the aluminum foil current collector.Electrolyte 1mol/l LiClO 4/ EC+DEC (1: 1 vol.), lithium metal do electrode, and U.S. Celgard2400 is a barrier film, is assembled into simulated battery in the glove box of applying argon gas.Current density 0.4mA/cm 2Constant current charge-discharge, deboost 3.3～4.35V.Material is discharge capacity 120mAh/g first, and efficient is 98%.Circulating, discharge capacity is 116.5mAh/g after 10 times.
Embodiment 2
Except doing the reaction medium with oxalic acid, other condition is with embodiment 1.Material is discharge capacity 118.2mAh/g first, and efficient is 98%.Discharge capacity 114.7mAh/g after 20 times circulates.
Embodiment 3
Except doing the reaction medium with acetate, other condition is with embodiment 1.Material is discharge capacity 114mAh/g first, and efficient is 97.1%.Discharge capacity 110mAh/g after 20 times circulates.
Embodiment 4
Except adopting Li 2CO 3Outside the Li source, other condition is with embodiment 1.Record material discharge capacity 119.2mAh/g first, efficient is 98%.Discharge capacity 115.3mAh/g after 20 times circulates.
Embodiment 5
Except adopting metal M n powder to do the manganese source, other condition records material discharge capacity 117.9mAh/g first with embodiment 1, and efficient is 97.6%.Discharge capacity 114.2mAh/g after 20 times circulates.
Embodiment 6
Except rising to 750 ℃ with heat up naturally (non-temperature programmed control), other condition is with embodiment 1.Material is discharge capacity 113.8mAh/g first, and efficient is 97.5%.Discharge capacity 108.2mAh/g after 20 times circulates.
Embodiment 7
Except calcination atmosphere is an oxygen, outside the flow 40ml/min, other condition is with embodiment 1.Material is discharge capacity 121mAh/g first, and efficient is 98%.Discharge capacity 118mAh/g after 20 times circulates.Comparative Examples 1
Adopt solid-phase synthesis as a comparison case.With EMD and LiOH is initiation material, fully grinds between the material, mixes, and reaches the uniform purpose of batch mixing.With it at 750 ℃ of roasting 12h, natural cooling.The stereoscan photograph that obtains material is seen Fig. 3, and the synthetic material granule size of this method is not very even as can be seen, and the phenomenon of gathering is arranged between the particle.Material is discharge capacity 111mAh/g first, and efficient is 96.3%.Circulating, discharge capacity is 104mAh/g after 20 times.Comparative Examples 2
Grind except taking out behind the roasting 12h, outside the roasting 12h, other preparation condition is with Comparative Examples 1 again.Material is discharge capacity 115mAh/g first, and efficient is 97.5%.Circulating, discharge capacity is 112.4mAh/g after 20 times.Comparative Examples 3
Except using water as decentralized medium, other preparation condition is with Comparative Examples 1.Material is discharge capacity 111.3mAh/g first, and efficient is 96%.Circulating, discharge capacity is 106.3mAh/g after 20 times.

Claims (5)

1. synthetic lithium manganese oxide preparation methods, it is characterized in that Li salt and Mn source are dispersed in the organic acid solution, organic acid can be in acetate, ethanedioic acid, oxalic acid, the citric acid any one or a few, wherein the molar ratio of organic acid and manganese is 0.5～5, organic acid plays the effect of reactant and dispersant simultaneously, make between the material and evenly mix, the solution evaporate to dryness is obtained the gel presoma, obtain positive electrode after the roasting.
2. according to the positive electrode of claim 1, it is characterized in that the Mn source can be electrolytic manganese dioxide EMD, chemical manganese bioxide CMD, even can be the very high manganese metal of purity.
3. according to the positive electrode of claim 1, it is characterized in that roasting process carries out in two stages, phase I reaction temperature 300-500 ℃, 700-800 ℃ of second stage reaction temperature.
4. according to the positive electrode of claim 3, it is characterized in that phase I roasting time 1-6h, second stage roasting time 8-16h.
5. according to the positive electrode of claim 3, it is characterized in that controlling the lifting temperature is 0.5 ℃～10 ℃/min, guarantees that material is heated evenly in roasting process, prevents that the local overheating particle from reuniting.
CN00112964A 2000-05-25 2000-05-25 Process for preparing lithium manganese oxide as positive electrode of lithium ion battery Pending CN1326232A (en)

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1297020C (en) * 2002-12-24 2007-01-24 中国科学院青海盐湖研究所 Calicining process for high-quality lithium ion battery positive electrodes and calcining apparatus thereof
CN100364153C (en) * 2005-05-24 2008-01-23 中国科学院成都有机化学有限公司 Li4Ti5O12 cathode material cladden on surface of spinel LiMn2O4 and preparation method thereof
CN100403587C (en) * 2005-05-20 2008-07-16 中南大学 Doped and layered lithium ion secondary battery positive electrode material and preparation method thereof
CN100436333C (en) * 2004-08-31 2008-11-26 比亚迪股份有限公司 Lithium cell anode material lithium manganate preparing method
CN101807686A (en) * 2010-03-30 2010-08-18 兰州金里能源科技有限公司 Preparation method of spinel type lithium manganate with high crystallinity used in lithium ion battery
CN101967055A (en) * 2010-10-20 2011-02-09 河南联合新能源有限公司 Method for preparing Co-Ni-Mn ternary anode materials by microwave sintering
CN101582500B (en) * 2009-06-09 2011-03-30 厦门大学 Method for preparing anode material of metal oxide nano-sheet lithium ion battery
CN102723478A (en) * 2012-06-30 2012-10-10 北京化工大学 Octahedral lithium manganate micron single crystal electrode material and preparation method thereof
CN103022470A (en) * 2012-12-19 2013-04-03 苏州大学 AZO-coated lithium manganate cathode material for secondary lithium battery and preparation method of same
CN103730650A (en) * 2013-12-16 2014-04-16 广西科技大学 Battery cathode material and high temperature solid phase synthesis method
CN106745337A (en) * 2017-02-24 2017-05-31 安顺学院 A kind of LiNi1/3Co1/3Mn1/3O2Preparation method
CN110639507A (en) * 2019-09-27 2020-01-03 华南理工大学 Li-Mn bimetallic oxide composite denitration catalyst and preparation method and application thereof
WO2021226702A1 (en) * 2020-05-14 2021-11-18 Nano One Materials Corp. Alternative method for making lithium battery cathode materials
CN114975931A (en) * 2022-05-31 2022-08-30 华南师范大学 Organic acid derived carbon modified manganese oxide composite material and preparation method and application thereof
WO2024039915A1 (en) 2022-08-19 2024-02-22 Novonix Battery Technology Solutions Inc. Methods for preparing lithium transition metal oxide from elemental metal feedstocks and products thereof

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1297020C (en) * 2002-12-24 2007-01-24 中国科学院青海盐湖研究所 Calicining process for high-quality lithium ion battery positive electrodes and calcining apparatus thereof
CN100436333C (en) * 2004-08-31 2008-11-26 比亚迪股份有限公司 Lithium cell anode material lithium manganate preparing method
CN100403587C (en) * 2005-05-20 2008-07-16 中南大学 Doped and layered lithium ion secondary battery positive electrode material and preparation method thereof
CN100364153C (en) * 2005-05-24 2008-01-23 中国科学院成都有机化学有限公司 Li4Ti5O12 cathode material cladden on surface of spinel LiMn2O4 and preparation method thereof
CN101582500B (en) * 2009-06-09 2011-03-30 厦门大学 Method for preparing anode material of metal oxide nano-sheet lithium ion battery
CN101807686A (en) * 2010-03-30 2010-08-18 兰州金里能源科技有限公司 Preparation method of spinel type lithium manganate with high crystallinity used in lithium ion battery
CN101967055A (en) * 2010-10-20 2011-02-09 河南联合新能源有限公司 Method for preparing Co-Ni-Mn ternary anode materials by microwave sintering
CN102723478A (en) * 2012-06-30 2012-10-10 北京化工大学 Octahedral lithium manganate micron single crystal electrode material and preparation method thereof
CN103022470A (en) * 2012-12-19 2013-04-03 苏州大学 AZO-coated lithium manganate cathode material for secondary lithium battery and preparation method of same
CN103022470B (en) * 2012-12-19 2016-01-20 苏州大学 AZO coating LiMn 2 O positive pole material of secondary lithium battery and preparation method thereof
CN103730650A (en) * 2013-12-16 2014-04-16 广西科技大学 Battery cathode material and high temperature solid phase synthesis method
CN103730650B (en) * 2013-12-16 2016-08-17 广西科技大学 A kind of cell positive material and high temperature process heat method thereof
CN106745337A (en) * 2017-02-24 2017-05-31 安顺学院 A kind of LiNi1/3Co1/3Mn1/3O2Preparation method
CN110639507A (en) * 2019-09-27 2020-01-03 华南理工大学 Li-Mn bimetallic oxide composite denitration catalyst and preparation method and application thereof
WO2021226702A1 (en) * 2020-05-14 2021-11-18 Nano One Materials Corp. Alternative method for making lithium battery cathode materials
CN115605438A (en) * 2020-05-14 2023-01-13 加拿大商纳诺万麦帝瑞尔公司（Ca） Alternative method for manufacturing cathode material for lithium battery
JP7426506B2 (en) 2020-05-14 2024-02-01 ナノ ワン マテリアルズ コーポレーション Alternative ways to make lithium battery cathode materials
CN114975931A (en) * 2022-05-31 2022-08-30 华南师范大学 Organic acid derived carbon modified manganese oxide composite material and preparation method and application thereof
WO2024039915A1 (en) 2022-08-19 2024-02-22 Novonix Battery Technology Solutions Inc. Methods for preparing lithium transition metal oxide from elemental metal feedstocks and products thereof

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