CN104157870A - Two-step high-energy ball milling method for preparation of lithium manganate solid solution anode material rich in lithium - Google Patents

Two-step high-energy ball milling method for preparation of lithium manganate solid solution anode material rich in lithium Download PDF

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Publication number
CN104157870A
CN104157870A CN201410395886.4A CN201410395886A CN104157870A CN 104157870 A CN104157870 A CN 104157870A CN 201410395886 A CN201410395886 A CN 201410395886A CN 104157870 A CN104157870 A CN 104157870A
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lithium
ball
solid solution
sintering
compound
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孙琦
李岩
孙慧英
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QINGDAO QIANYUN HIGH-TECH NEW MATERIAL Co Ltd
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QINGDAO QIANYUN HIGH-TECH NEW MATERIAL Co Ltd
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection 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
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection 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
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention relates to a preparation method of lithium manganate solid solution rich in lithium, and in particular relates to a two-step of high-energy ball milling method for the preparation of a lithium manganate solid solution rich in lithium. The method is as below: crushing and mixing one of nickel compound and cobalt compound, or two manganese compounds; mixing with zirconia ball in a ball mill; then sintering to obtain a solid solution; then crushing the solid solution and lithium compound, and mixing with zirconium balls in ball mill; and finally sintering to obtain the lithium manganate solid solution anode material rich in lithium. The invention has the following advantages: (1) high-energy ball milling is conducive to lowering reaction activation energy and the occurrence of solid state reaction; (2) the solid phase method has the advantages of simple process, low cost and easiness for industrialized production; and (3) a two-step sintering is employed: first conducting ball milling on a nickel, cobalt and manganese compound, pre-sintering, reacting to form a solid solution precursor of the three, and then adding lithium into the precursor for secondary ball milling, and sintering; and the two-step sintering is conducive to the even distribution of lithium in each phase.

Description

A kind of two step high-energy ball millings are prepared the method for rich lithium lithium manganese oxide solid solution cathode material
Technical field
The present invention relates to a kind of preparation method of rich lithium lithium manganese oxide solid solution cathode material, be specifically related to a kind of method that two step high-energy ball millings are prepared rich lithium lithium manganese oxide solid solution cathode material.
Background technology
Lithium ion battery, as a kind of novel secondary cell, has the advantages that specific capacity is high, voltage is high, fail safe is good.Be not only in automobile industry, in many-sides such as electronic equipment, national defense industry, field of aerospace, military science and technology, also have broad application prospects, become the focus that people pay close attention to.
Electrode material is core and the key technology of lithium ion battery, and therefore, the research and development of new electrode materials just becomes one of lithium ion battery main research.LiCoO 2although be one of the most ripe material of current commercialization, there is poor stability, overcharge resistance performance is poor, cost is high and the problems such as pollution to environment; And LiNiO 2same existence and stability is poor, easily causes safety problem, and need under oxygen atmosphere, synthesize, and cation mixing easily occurs in building-up process and generate non-stoichiometry structural compounds.Manganese is LiMn 2o 4easily there is dissolving and the Jahn-Teller effect of crystal transfer and manganese ion in positive electrode, cause battery capacity decay serious, and its reversible capacity can only reach 110mAh/g left and right in cyclic process.Although stratiform ternary material Li-Ni-Co-Mn-O has effectively made up LiCoO 2, LiNiO 2and LiMn 2o 4deficiency separately, but specific capacity is still below 200mAh/g.Research is found, if add excessive lithium in this class layered oxide material, obtains the rich lithium manganate cathode material for lithium of a kind of novel solid solution, and the specific capacity of this material is greater than 200mAh/g, is 2 times of left and right of current positive electrode actual capacity used.This material with high power capacity, low cost, compared with stable structure advantage, in stratified material system, be subject to widely paying close attention to, become gradually this domain expert scholar's study hotspot.
At present, the preparation method of lithium-rich manganese-based anode material mainly contain that solid phase is synthetic, liquid phase coprecipitation, sol-gel and spraying dry.Publication number is that the Chinese patent of CN102544475A discloses a kind of preparation method who prepares rich lithium lithium manganese oxide solid solution cathode material by oxalate coprecipitation.Coprecipitation is generally that then the hydroxide presoma of first preparing composite transition metal ion carries out roasting by presoma and lithium salts.Although this preparation method can improve being uniformly distributed of ion, but the synthetic technique of coprecipitation is loaded down with trivial details, stoichiometry is wayward, higher to equipment requirement, and if strictly do not controlled experiment condition, the bivalent metal ion in hydroxide is easy to oxidizedly, and then causes the oxide dephasign that occurs different valence state manganese in end product, has affected to a certain extent the chemical property of this material.Publication number is that the Chinese patent of CN102255069A discloses a kind of lithium-enriched cathodic material of lithium ion battery and preparation method thereof, comprise the steps: that lithium salts, transition metal salt and gelatinizing agent react and obtain colloidal sol in solvent, after colloidal sol is dried, after presintering and sintering, obtain successively described positive electrode.Publication number is that the Chinese patent of CN102891308A discloses a kind of method of utilizing spray drying granulation, and is coated with conducting polymer, obtains a kind of lithium-enriched cathodic material of lithium ion battery.The dry production cost of sol-gel and spraying is higher, is unsuitable for suitability for industrialized production.
Application number is that 200910303612.7 patent discloses a kind of preparation method who prepares composite anode material of high-capacity lithium ion battery by a single-step solid phase reaction, but a this single-step solid phase reaction is unfavorable for being uniformly distributed of lithium ion.
Summary of the invention
According to above the deficiencies in the prior art, the object of the invention is to find a kind of technique simple, cost is low, is easy to suitability for industrialized production and electrochemical properties homogeneous, stable production method, specifically provides a kind of two step high-energy ball millings to prepare the method for rich lithium lithium manganese oxide solid solution cathode material.
A kind of two step high-energy ball millings of the present invention are prepared the method for rich lithium lithium manganese oxide solid solution cathode material, one or both in nickel compound or cobalt compound are mixed at ball mill with zirconium ball after being pulverized and mixed with manganese compound, then sintering obtains solid solution, solid solution is mixed at ball mill with zirconium ball after crushed with lithium compound, last sintering obtains rich lithium lithium manganese oxide solid solution cathode material again.
Wherein, preferred version is as follows:
Nickel compound is oxide or the hydroxide of nickel; Cobalt compound is oxide or the hydroxide of cobalt; The oxide of the manganese that manganese compound is or hydroxide, more preferably electrolytic manganese dioxide; Lithium compound Li 2cO 3or LiOH.Selecting of above nickel source, cobalt source, He Li source, manganese source selected for the routine of this area, and the quantity relative ratio relationship between each material is also according to selecting within the scope of art technology.
When in ball mill, ball milling mixes, ball material volume ratio is 5:1-20:1, and the diameter of zirconium ball is 3-10mm.
The sintering temperature of solid solution is 400-700 ℃, sintering time 3-8h.
Solid solution mixes at ball mill with zirconium ball after crushed with lithium compound, finally by good material pre-burning 4-10h, the 800-1000 ℃ of sintering 10-25h at 500-700 ℃ of ball milling, in sintering process, pass into air, sintering complete cooling, grind after sieving and obtain rich lithium lithium manganese oxide solid solution cathode material.
More particularly preferably according to following steps, prepare:
(1) batch mixing: by nickel compound or cobalt compound one or both with manganese compound for pulverizer pulverize, mix 1-5h, pulverize D50=3-7um afterwards;
(2) ball milling: be 5:1-20:1 by above-mentioned compound and zirconium ball according to ball material volume ratio, put into ball mill mixing 3-20h, wherein the diameter of zirconium ball is 3-10mm, the frequency that ball milling rotates is 20-50Hz;
(3) once sintered: the good material of ball milling, at 400-700 ℃ of sintering 3-8h, is obtained to solid solution;
(4) rerolling: solid solution pulverizes, mixes 1-5h in micromill with lithium compound, D50=2-6um after pulverizing;
(5) secondary ball milling: be 5:1-20:1 by above-mentioned compound and zirconium ball according to ball material volume ratio, put into ball mill mixing 3-20h, wherein the diameter of zirconium ball is 3-10mm, the frequency that ball milling rotates is 20-50Hz;
(6) double sintering: by good material pre-burning 4-10h, the 800-1000 ℃ of sintering 10-25h at 500-700 ℃ of ball milling, in sintering process, pass into air, sintering complete cooling, grind after sieving and obtain rich lithium lithium manganese oxide solid solution cathode material.
Existing coprecipitation method technique is loaded down with trivial details, and stoichiometry is wayward, higher to equipment and requirement for experiment condition; Sol-gel and spray drying process production cost are higher, are unsuitable for suitability for industrialized production; One single-step solid phase reaction is unfavorable for being uniformly distributed of elemental lithium.And the present invention adopts two step ball millings to mix and the solid phase method of two-step sintering, have the following advantages: (1) high-energy ball milling is conducive to reduce the reaction activity of material, be conducive to the generation of solid phase reaction.(2) solid phase method technique is simple, and cost is low, is easy to suitability for industrialized production.(3) adopt two-step sintering: first by presintering after the compound ball milling of nickel, cobalt, manganese, reaction forms three's solid solution presoma, then this presoma is added to lithium secondary ball milling sintering, be conducive to elemental lithium at each being uniformly distributed in mutually.
Accompanying drawing explanation
Fig. 1 is the ESEM picture (left side is low power figure, and right side is high power figure) that embodiment 1 prepares product;
Fig. 2 is the particle diameter distribution map that embodiment 1 prepares product;
Fig. 3 is the XRD figure that embodiment 1 prepares product;
Fig. 4 is that embodiment 1 prepares the charge-discharge test curve chart that product is made button cell.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention will be further described.
Embodiment 1:
Get the EMD (electrolytic manganese dioxide) and 93g Ni (OH) of 261g 2in micromill, mix 2h, the D50=5.43um of compound mixes 8h by compound with the zirconium ball (diameter 6mm) of 10 times of volumes in ball mill, and the frequency that ball milling rotates is 30Hz, then sintering 5h at 600 ℃, after burning-out by the Li of above-mentioned material and 222g 2cO 3according to above-mentioned steps, carry out rerolling, secondary ball milling, finally carries out double sintering, and at 650 ℃, pre-burning 5h is then warming up to 950 ℃ of sintering 20h, in sintering process, pass into air, sintering complete cooling, grind after sieving and obtain rich lithium lithium manganese oxide solid solution cathode material Li 1.2ni 0.2mn 0.6o 2.
Fig. 1 is the ESEM picture of this product, and this product of Image Display is comprised of with evenly tiny second particle the spherical primary particle of class.Fig. 2 is the particle diameter distribution map of product, and D50 is 7.94um.Fig. 3 is the XRD figure of product, and the crystallinity of Image Display product is good, and one group of peak splitting between 60 °-70 ° is obvious, illustrates that this lithium-rich anode material layer structure is good.Fig. 4 is the charge-discharge test curve chart that product is made button cell, in test voltage interval, is 2.0-4.75V, and under the condition that measuring current is 0.3C, the first discharge specific capacity of this material is 258mAh/g.
Embodiment 2:
Get EMD (electrolytic manganese dioxide), the 93g Ni (OH) of 217.5g 2co (OH) with 46.5g 2, in micromill, mix 2h, the D50=5.20um of compound, compound is mixed to 8h with the zirconium ball (diameter 4mm) of 15 times of volumes in ball mill, the frequency that ball milling rotates is 25Hz, sintering 8h at 500 ℃ then, after burning-out by the Li of above-mentioned material and 222g 2cO 3according to above-mentioned steps, carry out rerolling, secondary ball milling, finally carries out double sintering, and at 550 ℃, pre-burning 10h is then warming up to 900 ℃ of sintering 20h, in sintering process, pass into air, sintering complete cooling, grind after sieving and obtain rich lithium lithium manganese oxide solid solution cathode material Li 1.2ni 0.2co 0.1mn 0.5o 2.
Embodiment 3:
Get EMD (electrolytic manganese dioxide), the 69.75g Ni (OH) of 261g 2co (OH) with 46.5g 2in micromill, mix 2h, the D50=6.61um of compound, compound is mixed to 5h with the zirconium ball (diameter 5mm) of 15 times of volumes in ball mill, the frequency that ball milling rotates is 40Hz, then sintering 8h at 500 ℃, after burning-out, the LiOH of above-mentioned material and 138g is carried out to rerolling according to above-mentioned steps, secondary ball milling, finally carry out double sintering, at 550 ℃, pre-burning 10h is then warming up to 1000 ℃ of sintering 15h, passes into air in sintering process, sintering complete cooling, grind after sieving and obtain rich lithium lithium manganese oxide solid solution cathode material Li 1.15ni 0.15co 0.1mn 0.6o 2.

Claims (9)

1. a step high-energy ball milling is prepared the method for rich lithium lithium manganese oxide solid solution cathode material, it is characterized in that one or both in nickel compound or cobalt compound to mix at ball mill with zirconium ball after being pulverized and mixed with manganese compound, then sintering obtains solid solution, solid solution is mixed at ball mill with zirconium ball after crushed with lithium compound, last sintering obtains rich lithium lithium manganese oxide solid solution cathode material again.
2. a kind of two step high-energy ball millings according to claim 1 are prepared the method for rich lithium lithium manganese oxide solid solution cathode material, it is characterized in that nickel compound is oxide or the hydroxide of nickel.
3. a kind of two step high-energy ball millings according to claim 1 are prepared the method for rich lithium lithium manganese oxide solid solution cathode material, it is characterized in that cobalt compound is oxide or the hydroxide of cobalt.
4. a kind of two step high-energy ball millings according to claim 1 are prepared the method for rich lithium lithium manganese oxide solid solution cathode material, it is characterized in that manganese compound is oxide or the hydroxide of manganese.
5. a kind of two step high-energy ball millings according to claim 1 are prepared the method for rich lithium lithium manganese oxide solid solution cathode material, it is characterized in that lithium compound Li 2cO 3or LiOH.
6. a kind of two step high-energy ball millings according to claim 1 are prepared the method for rich lithium lithium manganese oxide solid solution cathode material, and while it is characterized in that in ball mill, ball milling mixes, ball material volume ratio is 5:1-20:1, and the diameter of zirconium ball is 3-10mm.
7. a kind of two step high-energy ball millings according to claim 1 are prepared the method for rich lithium lithium manganese oxide solid solution cathode material, and the sintering temperature that it is characterized in that solid solution is 400-700 ℃, sintering time 3-8h.
8. a kind of two step high-energy ball millings according to claim 1 are prepared the method for rich lithium lithium manganese oxide solid solution cathode material, it is characterized in that solid solution mixes at ball mill with zirconium ball after crushed with lithium compound, finally by good material pre-burning 4-10h, the 800-1000 ℃ of sintering 10-25h at 500-700 ℃ of ball milling, in sintering process, pass into air, sintering complete cooling, grind after sieving and obtain rich lithium lithium manganese oxide solid solution cathode material.
9. according to a kind of two step high-energy ball millings described in claim 1~8, prepare the method for rich lithium lithium manganese oxide solid solution cathode material, it is characterized in that preparing according to following steps:
(1) batch mixing: by nickel compound or cobalt compound one or both with manganese compound for pulverizer pulverize, mix 1-5h, pulverize D50=3-7um afterwards;
(2) ball milling: be 5:1-20:1 by above-mentioned compound and zirconium ball according to ball material volume ratio, put into ball mill mixing 3-20h, wherein the diameter of zirconium ball is 3-10mm, the frequency that ball milling rotates is 20-50Hz;
(3) once sintered: the good material of ball milling, at 400-700 ℃ of sintering 3-8h, is obtained to solid solution;
(4) rerolling: solid solution pulverizes, mixes 1-5h in micromill with lithium compound, D50=2-6um after pulverizing;
(5) secondary ball milling: be 5:1-20:1 by above-mentioned compound and zirconium ball according to ball material volume ratio, put into ball mill mixing 3-20h, wherein the diameter of zirconium ball is 3-10mm, the frequency that ball milling rotates is 20-50Hz;
(6) double sintering: by good material pre-burning 4-10h, the 800-1000 ℃ of sintering 10-25h at 500-700 ℃ of ball milling, in sintering process, pass into air, sintering complete cooling, grind after sieving and obtain rich lithium lithium manganese oxide solid solution cathode material.
CN201410395886.4A 2014-08-13 2014-08-13 Two-step high-energy ball milling method for preparation of lithium manganate solid solution anode material rich in lithium Pending CN104157870A (en)

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