CN106953094A - A kind of high circulation, high voltage are modified the preparation method of rich lithium manganate cathode material for lithium - Google Patents

A kind of high circulation, high voltage are modified the preparation method of rich lithium manganate cathode material for lithium Download PDF

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Publication number
CN106953094A
CN106953094A CN201611263678.4A CN201611263678A CN106953094A CN 106953094 A CN106953094 A CN 106953094A CN 201611263678 A CN201611263678 A CN 201611263678A CN 106953094 A CN106953094 A CN 106953094A
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lithium
manganate cathode
modified
obtains
manganese
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CN201611263678.4A
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徐茂龙
黄红如
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HUIZHOU LONGWAYCAP TECHNOLOGY Co Ltd
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HUIZHOU LONGWAYCAP TECHNOLOGY Co Ltd
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    • H—ELECTRICITY
    • H01—BASIC 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

Abstract

The present invention provides the preparation method that a kind of high circulation, high voltage are modified rich lithium manganate cathode material for lithium, comprises the following steps：(1) spheric manganese carbonate will be obtained after the aqueous solution combination drying of the aqueous solution of manganese salt and carbonate；(2) spherical manganese dioxide will be obtained；(3) spherical manganese dioxide is calcined in lithium hydroxide mixing, obtains Li2MnO4；(4) by Li2MnO4It is added in manganese chloride solution, and stir, drying obtains precursor product, (5) sintering obtains modified rich lithium manganate cathode material for lithium, the present invention provide the preparation method that a kind of high circulation, high voltage be modified rich lithium manganate cathode material for lithium have efficiently, quick, energy-conservation the characteristics of, and the modified rich lithium manganate cathode material for lithium synthesized by the synthetic method has the advantages that capacity height, high-temperature stable, good cycle, compacted density height, charging rate are fast, and this method technique is simple, environment-friendly, suitable high-volume industry is produced.

Description

A kind of high circulation, high voltage are modified the preparation method of rich lithium manganate cathode material for lithium
Technical field
The present invention relates to a kind of method for preparing anode material, and in particular to a kind of high circulation, high voltage are modified rich lithium mangaic acid The preparation method of lithium anode material.
Background technology
Manganese-based anode material has price low, the advantages of green non-pollution, is the research emphasis of lithium ion battery.In manganese base In positive electrode, that studies more has spinelle Li2MnO3, stratiform LiMnO2With layed solid-solution positive electrode, pure rich lithium LiMn2O4 Li2MnO3It is also denoted as Li (Li1/3Mn2/3)O2, with layer structure, Li is appeared in transition metal layer, with Mn (according to Li：Mn=1：2) structure of superstructure is formd, because Mn therein has been+4 valencys, in the range of normal discharge and recharge (2.0-4.4V), Mn4+It is difficult to followed by valency of continuing rising, Li2MnO3Show non-electroactive.But when the scope of discharge and recharge is expanded to During 2.0-4.8V, Li2MnO3It can show electroactive, but in initial charge, O is along with Li+Deviate from together, Li2MnO3Reason 438mAh/g is can reach by specific capacity, and with good heat endurance, but because Mechanism of electrochemical behaviors of anhydrous is special, material first can not Inverse capacity is big, and cycle performance is poor, and electric conductivity and high rate performance are poor, is not suitable for being used alone, therefore needs further improvement.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of efficient longevity for above-mentioned the deficiencies in the prior art Life, the preparation method of Hyperhemodynamics type manganate cathode material for lithium.
The present invention provides the preparation method that a kind of high circulation, high voltage are modified rich lithium manganate cathode material for lithium, including as follows Step：
(1) carbonic acid for being 2mol/L~8mol/L by the aqueous solution and concentration that concentration is 0.05mol/L~3mol/L manganese salts The aqueous solution mixing of salt, stirring reaction 15min obtains spheric manganese carbonate after separation, washing, drying；
(2) gained spheric manganese carbonate in step (1) is dispersed in water and obtains dispersion liquid, be added dropwise into the dispersion liquid dense Spend the liquor potassic permanganate for 3mol/L, diluted acid is added dropwise in 1~3min of stirring, react 1~3min, separation, washing, dry after obtain Spherical manganese dioxide；
(3) spherical manganese dioxide is calcined in lithium hydroxide mixing, obtains Li2MnO4；
(4) by resulting Li in step (3)2MnO4It is added in manganese chloride solution, stirs, while adds Al2O3、 Sc2O3With Ce O2Powder, and stir, drying obtains precursor product,
(5) the presoma body product obtained in step (4) is sintered and obtains modified rich lithium manganate cathode material for lithium.
Further, the modified rich lithium manganate cathode material for lithium obtained in step (4) meets chemical formula：In step (4) To modified rich lithium manganate cathode material for lithium meet chemical formula：Li2(MnwAlzScy Cex)O4, wherein 6w+4x+3y+3z=6.
The beneficial effects of the present invention are：
The present invention provide the preparation method that a kind of high circulation, high voltage be modified rich lithium manganate cathode material for lithium have efficiently, Quickly, the characteristics of energy-conservation, and the modified rich lithium manganate cathode material for lithium synthesized by the synthetic method has capacity height, high temperature steady The advantages of fixed, good cycle, compacted density are high, charging rate is fast, and this method technique is simple, environment-friendly, it is large quantities of to be adapted to Amount industry is produced.
Embodiment
Lower mask body illustrates embodiments of the present invention, and only for reference and explanation is used, and does not constitute and patent of the present invention is protected Protect the limitation of scope.
Embodiment 1
The present embodiment provides the preparation method that a kind of high circulation, high voltage are modified rich lithium manganate cathode material for lithium, including such as Lower step：
(1) carbonic acid for being 2mol/L~8mol/L by the aqueous solution and concentration that concentration is 0.05mol/L~3mol/L manganese salts The aqueous solution mixing of salt, stirring reaction 15min obtains spheric manganese carbonate after separation, washing, drying；
(2) gained spheric manganese carbonate in step (1) is dispersed in water and obtains dispersion liquid, be added dropwise into the dispersion liquid dense Spend the liquor potassic permanganate for 3mol/L, diluted acid is added dropwise in 1~3min of stirring, react 1~3min, separation, washing, dry after obtain Spherical manganese dioxide；
(3) spherical manganese dioxide is calcined in lithium hydroxide mixing, obtains Li2MnO4；
(4) by resulting Li in step (3)2MnO4It is added in manganese chloride solution, stirs, while adds Al2O3、 Sc2O3With Ce O2Powder, and stir, drying obtains precursor product,
(5) the presoma body product obtained in step (4) is sintered and obtains modified rich lithium manganate cathode material for lithium.
In the present embodiment, the modified rich lithium manganate cathode material for lithium obtained in step (4) meets chemical formula：In step (4) Obtained modified rich lithium manganate cathode material for lithium Li2(Mn0.5Al0.1Sc0.1Ce0.6)O4。
Test result shows that, in charging/discharging voltage 2.0-4.75V, charge-discharge magnification is under the conditions of 0.5C, electric discharge first is compared Capacity is 220mAh/g, circulates 500 capability retentions up to 80%；
Under conditions of charge-discharge magnification is 1C, first discharge specific capacity is 210mAh/g, circulates 500 capability retentions Up to 81%；
Under conditions of charge-discharge magnification is 4C, first discharge specific capacity is 205mAh/g, circulates 500 capability retentions Up to 78%.
Embodiment 2
The present embodiment provides the preparation method that a kind of high circulation, high voltage are modified rich lithium manganate cathode material for lithium, including such as Lower step：
(1) carbonic acid for being 2mol/L~8mol/L by the aqueous solution and concentration that concentration is 0.05mol/L~3mol/L manganese salts The aqueous solution mixing of salt, stirring reaction 15min obtains spheric manganese carbonate after separation, washing, drying；
(2) gained spheric manganese carbonate in step (1) is dispersed in water and obtains dispersion liquid, be added dropwise into the dispersion liquid dense Spend the liquor potassic permanganate for 3mol/L, diluted acid is added dropwise in 1~3min of stirring, react 1~3min, separation, washing, dry after obtain Spherical manganese dioxide；
(3) spherical manganese dioxide is calcined in lithium hydroxide mixing, obtains Li2MnO4；
(4) by resulting Li in step (3)2MnO4It is added in manganese chloride solution, stirs, while adds Al2O3、 Sc2O3With Ce O2Powder, and stir, drying obtains precursor product,
(5) the presoma body product obtained in step (4) is sintered and obtains modified rich lithium manganate cathode material for lithium.
In the present embodiment, the modified rich lithium manganate cathode material for lithium obtained in step (4) meets chemical formula：In step (4) Obtained modified rich lithium manganate cathode material for lithium Li2(Mn0.5Al0.2Sc0.2Ce0.45)O4。
Test result shows that, in charging/discharging voltage 2.0-4.75V, charge-discharge magnification is under the conditions of 0.5C, electric discharge first is compared Capacity is 300mAh/g, circulates 500 capability retentions up to 95%；
Under conditions of charge-discharge magnification is 1C, first discharge specific capacity is 280mAh/g, circulates 500 capability retentions Up to 81%；
Under conditions of charge-discharge magnification is 4C, first discharge specific capacity is 260mAh/g, circulates 500 capability retentions Up to 78%.
Embodiment 3
The present embodiment provides the preparation method that a kind of high circulation, high voltage are modified rich lithium manganate cathode material for lithium, including such as Lower step：
(1) carbonic acid for being 2mol/L~8mol/L by the aqueous solution and concentration that concentration is 0.05mol/L~3mol/L manganese salts The aqueous solution mixing of salt, stirring reaction 15min obtains spheric manganese carbonate after separation, washing, drying；
(2) gained spheric manganese carbonate in step (1) is dispersed in water and obtains dispersion liquid, be added dropwise into the dispersion liquid dense Spend the liquor potassic permanganate for 3mol/L, diluted acid is added dropwise in 1~3min of stirring, react 1~3min, separation, washing, dry after obtain Spherical manganese dioxide；
(3) spherical manganese dioxide is calcined in lithium hydroxide mixing, obtains Li2MnO4；
(4) by resulting Li in step (3)2MnO4It is added in manganese chloride solution, stirs, while adds Al2O3、 Sc2O3With Ce O2Powder, and stir, drying obtains precursor product,
(5) the presoma body product obtained in step (4) is sintered and obtains modified rich lithium manganate cathode material for lithium.
In the present embodiment, the modified rich lithium manganate cathode material for lithium obtained in step (4) meets chemical formula：In step (4) Obtained modified rich lithium manganate cathode material for lithium Li2(Mn0.5Al0.3Sc0.3Ce0.3)O4。
Test result shows that, in charging/discharging voltage 2.0-4.75V, charge-discharge magnification is under the conditions of 0.5C, electric discharge first is compared Capacity is 350mAh/g, circulates 500 capability retentions up to 96%；
Under conditions of charge-discharge magnification is 1C, first discharge specific capacity is 330mAh/g, circulates 500 capability retentions Up to 94%；
Under conditions of charge-discharge magnification is 4C, first discharge specific capacity is 300mAh/g, circulates 500 capability retentions Up to 790%.
The present invention provide the preparation method that a kind of high circulation, high voltage be modified rich lithium manganate cathode material for lithium have efficiently, Quickly, the characteristics of energy-conservation, and synthesized by the synthetic method high circulation, high voltage is modified rich lithium manganate cathode material for lithium has The advantages of capacity height, high-temperature stable, good cycle, compacted density are high, charging rate is fast.
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplification, Equivalent substitute mode is should be, is included within protection scope of the present invention.

Claims (2)

1. a kind of high circulation, high voltage are modified the preparation method of rich lithium manganate cathode material for lithium, it is characterised in that including following step Suddenly：
(1) carbonate for being 2mol/L~8mol/L by the aqueous solution and concentration that concentration is 0.05mol/L~3mol/L manganese salts The aqueous solution is mixed, stirring reaction 15min, and spheric manganese carbonate is obtained after separation, washing, drying；
(2) gained spheric manganese carbonate in step (1) is dispersed in water and obtains dispersion liquid, concentration is added dropwise into the dispersion liquid is 3mol/L liquor potassic permanganate, stirring 1~3min be added dropwise diluted acid, react 1~3min, separation, washing, dry after obtain spherical Manganese dioxide；
(3) spherical manganese dioxide is calcined in lithium hydroxide mixing, obtains Li2MnO4；
(4) by resulting Li in step (3)2MnO4It is added in manganese chloride solution, stirs, while adds Al2O3、Sc2O3 With Ce O2Powder, and stir, drying obtains precursor product,
(5) the presoma body product obtained in step (4) is sintered and obtains modified rich lithium manganate cathode material for lithium.
2. a kind of high circulation as claimed in claim 1, high voltage are modified the preparation method of rich lithium manganate cathode material for lithium, it is special Levy and be：The modified rich lithium manganate cathode material for lithium obtained in step (4) meets chemical formula：Li2(MnwAlz Scy Cex)O4, its Middle 6w+4x+3y+3z=6.
CN201611263678.4A 2016-12-30 2016-12-30 A kind of high circulation, high voltage are modified the preparation method of rich lithium manganate cathode material for lithium Pending CN106953094A (en)

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PCT/CN2017/110595 WO2018121101A1 (en) 2016-12-30 2017-11-10 Method for preparing high-cycle and high-voltage modified lithium-rich lithium manganate positive electrode material

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Cited By (2)

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CN108155376A (en) * 2017-12-28 2018-06-12 湖南佳纳能源科技有限公司 A kind of method for preparing anode material for lithium-ion batteries precursor
WO2018121101A1 (en) * 2016-12-30 2018-07-05 徐茂龙 Method for preparing high-cycle and high-voltage modified lithium-rich lithium manganate positive electrode material

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Publication number Priority date Publication date Assignee Title
CN110534734B (en) * 2019-08-16 2022-03-01 西安电子科技大学 Preparation method of surface-modified lithium-manganese-rich cathode material

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CN101152963A (en) * 2006-09-30 2008-04-02 江苏双登集团有限公司 Method for synthesizing doping lithium manganic acid
CN102544475A (en) * 2012-03-07 2012-07-04 湖北万润新能源科技发展有限公司 Method for preparing lithium-enriched lithium manganese oxide solid solution cathode material
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Publication number Priority date Publication date Assignee Title
WO2018121101A1 (en) * 2016-12-30 2018-07-05 徐茂龙 Method for preparing high-cycle and high-voltage modified lithium-rich lithium manganate positive electrode material
CN108155376A (en) * 2017-12-28 2018-06-12 湖南佳纳能源科技有限公司 A kind of method for preparing anode material for lithium-ion batteries precursor

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