CN104319393A - Doping modification method of spinel lithium manganate anode material - Google Patents

Doping modification method of spinel lithium manganate anode material Download PDF

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CN104319393A
CN104319393A CN201410635501.7A CN201410635501A CN104319393A CN 104319393 A CN104319393 A CN 104319393A CN 201410635501 A CN201410635501 A CN 201410635501A CN 104319393 A CN104319393 A CN 104319393A
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lithium
citric acid
lithium manganate
doping
ball milling
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CN104319393B (en
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方道来
郑翠红
檀杰
闫勇
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Anhui University of Technology AHUT
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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
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection 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
    • 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 discloses a doping modification method of spinel lithium manganate anode material, and belongs to the field of nanotechnology. The method mainly comprises the following steps: respectively adding a saline solution of lithium-ion and doping ion into a citric acid solution, regulating pH values, adding ethylene glycol into the solution, heating and stirring the solution so as to form sol, mixing manganous-manganic oxide with the sol, performing ball milling, and performing microwave dehydration and subsequent heat treatment on products subjected to ball milling so as to obtain the doped spinel lithium manganate anode material. The method has the advantages that the prepared spinel lithium manganate anode material has high specific capacity, good rate capability and excellent cycling performance, meanwhile the technology is simple, the cost is low, the efficiency is high, and the method can be directly applied to industrial production.

Description

A kind of doping modification method of lithium manganate having spinel structure positive electrode
Technical field
The invention belongs to field of nanometer technology, relate to the colloidal sol-solid phase hydridization synthetic method of the spinel lithium manganate of a kind of preparation method of anode material for lithium-ion batteries, particularly unitary or binary metal ion doping.
Technical background
Lithium manganate having spinel structure has larger specific capacity (theoretical capacity 148mAhg -1) higher oxidation-reduction potential (4V vs.Li/Li +), with low cost, environmental friendliness and the advantage such as fail safe is good.As anode material for lithium-ion batteries, spinel lithium manganate is expected to the cobalt acid lithium of fictitious hosts costliness.But due to degradation reason under Mn ion-solubility, Jahn-Teller distortion and degree of crystallinity, spinel lithium manganese oxide anode material capacity attenuation in cyclic process is very serious, is particularly on active service at higher temperature (>=55 DEG C).Research shows, mixes other appropriate metal ions in spinel lithium manganate lattice, as metal ions such as Al, Co, Ni, Cr, Fe, Cu, Zr, Y, can realize the modification of LiMn2O4, can significantly improve its cycle performance.
At present, the synthetic method of the spinel lithium manganate of metal ion mixing has solid phase method and liquid phase method two class.Solid phase method is by the oxide of lithium source (lithium carbonate or lithium hydroxide), manganese source (being generally manganese dioxide or manganese carbonate) and Doped ions or salt mixing all, obtains the spinel lithium manganate of metal ion mixing through ball milling, low temperature calcination, high-temperature heat treatment.Although solid phase method technique is simple, chemical uniformity is poor, becomes phase temperature higher (>=800 DEG C), causes oxygen defect in lattice more.Therefore, the cycle performance of doped spinel LiMn2O4 that obtains of solid phase method is unsatisfactory.Liquid phase method mainly contains coprecipitation and sol-gal process.Coprecipitation is difficult to the stoichiometry of accurate controlled doping ion, and sol-gel process process is complicated, efficiency is low.These shortcomings of liquid phase method limit its application in the industrial production.
Summary of the invention
The present invention is directed to the above-mentioned shortcoming that existing technology of preparing exists, the new method of the spinel lithium manganate doping vario-property providing a kind of technique simple, with low cost, the method is applicable to preparing adulterated lithium manganate positive electrode in a large number.
The present invention is achieved by following technical scheme:
(1) by the chemical formula LiMn of the adulterated lithium manganate of preparation 2-xm xo 4take the required lithium source of metering, the salt of doped metal ion and citric acid, be mixed with the aqueous solution respectively, lithium source solution and doping metals salting liquid are joined in citric acid solution successively, with dust technology and weak aqua ammonia adjust ph to 5 ~ 6, add ethylene glycol again, stir 1 ~ 2h at 65 ~ 75 DEG C of constant temperature, form colloidal sol;
Described doping metals M is one in Al, Ni, Co, Cr, Fe, Cu, Zr and Y or two kinds, and doping x is 0.025 ~ 0.10; Described lithium source is the one in lithium hydroxide, lithium nitrate and lithium acetate; Described doped metal salt is nitrate or acetate; The consumption of described citric acid is 0.5 ~ 1.0 times of the total mole number of lithium ion and doped metal ion, and ethylene glycol consumption is 0.3 ~ 1.0 times of citric acid molal quantity; In described colloidal sol, the total concentration of metal ion controls at 0.3 ~ 1.0mol/L;
(2) the mangano-manganic oxide powder of required metering is joined in above-mentioned colloidal sol, mix, ball milling 2 ~ 3h;
Described mangano-manganic oxide powder primary particle size≤200nm, specific area>=10m 2/ g; Described mechanical milling process, adopts planetary ball mill, and use polytetrafluoroethylene material spherical tank and zirconium dioxide abrading-ball, abrading-ball is 5 ~ 9:1 with mangano-manganic oxide powder quality ratio, rotating speed 250rpm;
(3) microwave heating is carried out to the paste product that ball milling obtains, realize fast dewatering, thermal decomposition;
Described microwave heating implements in unlimited system, the power >=1000W used, till microwave heating process lasts till powder generation spontaneous combustion;
(4) by the product of Microwave Treatment in air atmosphere, 450 DEG C calcining 5h, subsequently ball milling 1 ~ 2h, then in air atmosphere, 550 ~ 650 DEG C of heat treatment 10 ~ 15h, obtain adulterate Spinel manganate cathode material for lithium.
Compared with prior art, the present invention has following technique effect:
1, the stoichiometric accurate control of the LiMn2O4 to unitary or binary metal ion doping can be realized;
2, can realize obtaining well-crystallized, pure spinelle adulterated lithium manganate powder in lower reaction temperature (550 ~ 650 DEG C), and good dispersion, uniform particle sizes tiny (primary particle size≤200nm);
The chemical property with excellence of 3, obtained spinelle adulterated lithium manganate positive electrode;
4, preparation technology of the present invention is simple, with low cost, efficiency is high, can be directly used in suitability for industrialized production.
Accompanying drawing explanation
The LiMn of Fig. 1 prepared by the embodiment of the present invention 1 1.95co 0.05o 4x-ray diffraction (XRD) collection of illustrative plates.
The LiMn of Fig. 2 prepared by the embodiment of the present invention 1 1.95co 0.05o 4field emission scanning electron microscope (FESEM) picture.
The LiMn of Fig. 3 prepared by the embodiment of the present invention 1 1.95co 0.05o 4the simulated battery sample of positive electrode assembling is at the constant current charge-discharge curve of different multiplying.
The LiMn of Fig. 4 prepared by the embodiment of the present invention 1 1.95co 0.05o 4the room temperature (20 DEG C) that the simulated battery sample that positive electrode is assembled records in 1C multiplying power and high temperature (55 DEG C) cycle performance figure;
Note: the manufacture method of the simulated battery sample of test is, cobalt manganic acid lithium active material will be mixed, conductive black will mix make positive plate with Kynoar (PVDF) (mass ratio is 80:15:5), with lithium paper tinsel be negative plate, Celgard 2400 polypropylene porous film is for barrier film, be assembled into CR2025 button cell, the electrolyte of use is 1mol/L LiPF 6/ EC+DEC (EC and DEC volume ratio is 1:1).
The LiMn of Fig. 5 prepared by the embodiment of the present invention 2 1.90co 0.065al 0.035o 4x-ray diffraction (XRD) collection of illustrative plates.
The LiMn of Fig. 6 prepared by the embodiment of the present invention 2 1.90co 0.065al 0.035o 4field emission scanning electron microscope (FESEM) picture.
Fig. 7 prepared by the embodiment of the present invention 2 with LiMn 1.90co 0.065al 0.035o 4the simulated battery sample of positive electrode assembling is at the constant current charge-discharge curve of different multiplying.
Fig. 8 prepared by the embodiment of the present invention 2 with LiMn 1.90co 0.065al 0.035o 4the room temperature (20 DEG C) that the simulated battery sample that positive electrode is assembled records in 1C multiplying power and high temperature (55 DEG C) cycle performance figure;
Note: same Fig. 4 of manufacture method of the simulated battery sample of test.
Embodiment
Below in conjunction with drawings and Examples in detail the present invention is described in detail, but the present invention is not limited to following embodiment.
Embodiment 1
(1) by the chemical formula LiMn of adulterated lithium manganate 1.95co 0.05o 4, take lithium hydroxide (LiOHH 2o) 4.1941g, cobalt nitrate (Co (NO 3) 26H 2o) 1.4552g, citric acid (C 6h 8o 7h 2o) 11.0324g, is dissolved in lithium hydroxide, cobalt nitrate and citric acid respectively in 50mL deionized water, is mixed with solution, by citric acid solution magnetic agitation, first adds lithium hydroxide solution, then adds cobalt nitrate solution, with dust technology (HNO 3) and weak aqua ammonia (NH 3h 2o) adjust pH to 6, adds ethylene glycol (C 2h 6o 2) 1.6294g, stir 1h at 65 DEG C of constant temperature, form colloidal sol;
(2) by mangano-manganic oxide (Mn 3o 4) powder (primary particle size≤200nm, specific area>=10m 2/ g) 14.8727g joins in above-mentioned colloidal sol, mixes, and be placed in ball grinder, ball milling 3h, ratio of grinding media to material 5:1 on planetary ball mill, rotating speed is 250rpm;
(3) paste product microwave heating ball milling obtained, power 1000W, till being heated to powder burning;
(4) by the product of Microwave Treatment in air atmosphere, 450 DEG C calcining 5h, ball milling 2h, then in air atmosphere, 550 DEG C of heat treatment 10h, obtain adulterate Spinel manganate cathode material for lithium.
XRD collection of illustrative plates (Fig. 1) and FESEM photo (Fig. 2) display, the cobalt manganic acid lithium of mixing that this embodiment obtains is pure Spinel, and well-crystallized, uniform particle sizes, primary particle size is 100 ~ 200nm.Show at the constant current charge-discharge curve (Fig. 3) of different multiplying, during 0.2C, discharge capacity is 122mAhg -1, when multiplying power increases to 10C, discharge capacity is 90mAhg -1, capability retention is 74%.Cycle performance curve (Fig. 4) shows, and after 1C, room temperature (20 DEG C) constant current charge-discharge 200 circulation, capability retention is 96%; After 1C, high temperature (55 DEG C) constant current charge-discharge 100 circulation, capability retention is 93%.
Embodiment 2
(1) by the chemical formula LiMn of adulterated lithium manganate 1.91co 0.055al 0.035o 4, take lithium hydroxide (LiOHH 2o) 4.1941g, cobalt nitrate (Co (NO 3) 26H 2o) 1.6007g, aluminum nitrate (Al (NO 3) 39H 2o) 1.3130g, citric acid (C 6h 8o 7h 2o) 13.7431g, is dissolved in lithium hydroxide, cobalt nitrate, aluminum nitrate and citric acid respectively in 50mL deionized water, is mixed with solution, by citric acid solution magnetic agitation, first add lithium hydroxide solution, then add cobalt nitrate, aluminum nitrate solution, with dust technology (HNO 3) and weak aqua ammonia (NH 3h 2o) adjust pH to 5, adds ethylene glycol (C 2h 6o 2) 2.4356g, stir 1.5h at 70 DEG C of constant temperature, form colloidal sol;
(2) by mangano-manganic oxide (Mn 3o 4) powder (primary particle size≤200nm, specific area>=10m 2/ g) 14.5676g joins in above-mentioned colloidal sol, mixes, and be placed in ball grinder, ball milling 3h, ratio of grinding media to material 7:1 on planetary ball mill, rotating speed is 250rpm;
(3) paste product microwave heating ball milling obtained, power 1000W, till being heated to powder burning;
(4) by the product of Microwave Treatment in air atmosphere, 450 DEG C calcining 5h, ball milling 1h, then in air atmosphere, 650 DEG C of heat treatment 15h, obtain adulterate Spinel manganate cathode material for lithium.
XRD collection of illustrative plates (Fig. 5) and FESEM photo (Fig. 6) display, the LiMn2O4 of the cobalt aluminium doping that this embodiment obtains is pure Spinel, and well-crystallized, uniform particle sizes, primary particle size is 100 ~ 200nm.Show at the constant current charge-discharge curve (Fig. 7) of different multiplying, during 0.2C, discharge capacity is 108mAhg -1, when multiplying power increases to 10C, discharge capacity is 78mAhg -1, capability retention is 72%.Cycle performance curve (Fig. 8) shows, and after 1C, room temperature (20 DEG C) constant current charge-discharge 200 circulation, capability retention is 98%; After 1C, high temperature (55 DEG C) constant current charge-discharge 100 circulation, capability retention is 96%.
Embodiment 3
(1) by the chemical formula LiMn of adulterated lithium manganate 1.95ni 0.05o 4, take lithium nitrate (LiNO 3) 6.895g, nickel acetate (Ni (CH 3cOO) 24H 2o) 1.2442g, citric acid (C 6h 8o 7h 2o) 15.4519g, is dissolved in lithium nitrate, nickel acetate and citric acid respectively in 60mL deionized water, is mixed with solution, by citric acid solution magnetic agitation, adds lithium nitrate solution, then adds nickel acetate liquid, adds weak aqua ammonia (NH 3h 2o) adjust pH to 6, adds ethylene glycol (C 2h 6o 2) 1.3035g, stir 2h at 70 DEG C of constant temperature, form colloidal sol;
(2) by mangano-manganic oxide (Mn 3o 4) powder (primary particle size≤200nm, specific area>=10m 2/ g) 14.8727g joins in above-mentioned colloidal sol, mixes, and be placed in ball grinder, ball milling 2h, ratio of grinding media to material 9:1 on planetary ball mill, rotating speed is 250rpm;
(3) paste product microwave heating ball milling obtained, power 1000W, till being heated to powder burning;
(4) by the product of Microwave Treatment in air atmosphere, 450 DEG C calcining 5h, ball milling 2h, then in air atmosphere, 600 DEG C of heat treatment 15h, obtain the Spinel manganate cathode material for lithium mixing nickel.
The nickel ion doped of mixing that this embodiment obtains is pure Spinel, and well-crystallized, uniform particle sizes, primary particle size is 100 ~ 200nm.Mix with this simulated battery sample that nickel ion doped assembles for positive electrode, during 0.2C, discharge capacity is 106mAhg -1, when multiplying power increases to 10C, discharge capacity is 80mAhg -1, capability retention is 75%, and after 1C, room temperature (20 DEG C) constant current charge-discharge 200 circulation, capability retention is 99%; After 1C, high temperature (55 DEG C) constant current charge-discharge 100 circulation, capability retention is 97%.

Claims (1)

1. a doping modification method for lithium manganate having spinel structure positive electrode, is characterized in that, comprises the following steps:
(1) by the chemical formula LiMn of the adulterated lithium manganate of preparation 2-xm xo 4take the required lithium source of metering, the salt of doped metal ion and citric acid, be mixed with the aqueous solution respectively, lithium source solution and doping metals salting liquid are joined in citric acid solution successively, with dust technology and weak aqua ammonia adjust ph to 5 ~ 6, add ethylene glycol again, stir 1 ~ 2h at 65 ~ 75 DEG C of constant temperature, form colloidal sol;
Described doping metals M is one in Al, Ni, Co, Cr, Fe, Cu, Zr and Y or two kinds, and doping x is 0.025 ~ 0.10; Described lithium source is the one in lithium hydroxide, lithium nitrate and lithium acetate; Described doped metal salt is nitrate or acetate; The consumption of described citric acid is 0.5 ~ 1.0 times of the total mole number of lithium ion and doped metal ion; The consumption of described ethylene glycol is 0.3 ~ 1.0 times of citric acid molal quantity; In described colloidal sol, the total concentration of metal ion controls at 0.3 ~ 1.0mol/L;
(2) the mangano-manganic oxide powder of required metering is joined in above-mentioned colloidal sol, mix, ball milling 2 ~ 3h;
Described mangano-manganic oxide powder primary particle size≤200nm, specific area>=10m 2/ g; Described mechanical milling process, adopts planetary ball mill, and use polytetrafluoroethylene material spherical tank and zirconium dioxide abrading-ball, abrading-ball is 5 ~ 9:1 with mangano-manganic oxide powder quality ratio, rotating speed 250rpm;
(3) microwave heating is carried out to the paste product that ball milling obtains, realize fast dewatering, thermal decomposition;
Described microwave heating implements in unlimited system, the power >=1000W used, till microwave heating process lasts till powder generation spontaneous combustion;
(4) by the product of Microwave Treatment in air atmosphere, 450 DEG C calcining 5h, subsequently ball milling 1 ~ 2h, then in air atmosphere, 550 ~ 650 DEG C of heat treatment 10 ~ 15h, obtain adulterate Spinel manganate cathode material for lithium.
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107739057A (en) * 2017-11-03 2018-02-27 云南民族大学 A kind of preparation method of lithium manganate having spinel structure
CN107855074A (en) * 2017-11-28 2018-03-30 桂林电子科技大学 A kind of particle diameter thinning method that metal oxide materials are prepared using nitrate as raw material
CN108455676A (en) * 2018-03-28 2018-08-28 山东省科学院能源研究所 A kind of preparation method of anode material for lithium-ion batteries nano spinel LiMn2O4
CN109411744A (en) * 2018-10-31 2019-03-01 云南民族大学 A kind of method of magnesium doping preparation High-performance lithium manganate anode material
CN109437334A (en) * 2018-10-31 2019-03-08 云南民族大学 A kind of preparation method of high magnification nickel cobalt codope lithium manganate having spinel structure material
CN110474031A (en) * 2019-08-20 2019-11-19 齐鲁工业大学 A method of Copper-cladding Aluminum Bar mangano-manganic oxide composite material is prepared using polymeric complexing agent
CN112744866A (en) * 2020-12-29 2021-05-04 无锡晶石新型能源股份有限公司 Preparation method of lithium manganate with low specific surface area and large particle size
CN113003610A (en) * 2021-02-08 2021-06-22 华南协同创新研究院 Sodium ion battery positive electrode material lithium manganate and preparation method and application thereof
CN114105209A (en) * 2021-11-22 2022-03-01 江南大学 Doped modified lithium manganate lithium ion battery positive electrode material and preparation method thereof
CN114180635A (en) * 2021-10-28 2022-03-15 厦门理工学院 Single-crystal lithium manganate positive electrode material, preparation method and application

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CN103682312A (en) * 2013-12-10 2014-03-26 江西省钨与稀土产品质量监督检验中心（江西省钨与稀土研究院） Method used for preparing nickel-based layer structural ternary cathode material using microwave
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107739057A (en) * 2017-11-03 2018-02-27 云南民族大学 A kind of preparation method of lithium manganate having spinel structure
CN107855074A (en) * 2017-11-28 2018-03-30 桂林电子科技大学 A kind of particle diameter thinning method that metal oxide materials are prepared using nitrate as raw material
CN108455676A (en) * 2018-03-28 2018-08-28 山东省科学院能源研究所 A kind of preparation method of anode material for lithium-ion batteries nano spinel LiMn2O4
CN109411744A (en) * 2018-10-31 2019-03-01 云南民族大学 A kind of method of magnesium doping preparation High-performance lithium manganate anode material
CN109437334A (en) * 2018-10-31 2019-03-08 云南民族大学 A kind of preparation method of high magnification nickel cobalt codope lithium manganate having spinel structure material
CN110474031A (en) * 2019-08-20 2019-11-19 齐鲁工业大学 A method of Copper-cladding Aluminum Bar mangano-manganic oxide composite material is prepared using polymeric complexing agent
CN112744866A (en) * 2020-12-29 2021-05-04 无锡晶石新型能源股份有限公司 Preparation method of lithium manganate with low specific surface area and large particle size
CN113003610A (en) * 2021-02-08 2021-06-22 华南协同创新研究院 Sodium ion battery positive electrode material lithium manganate and preparation method and application thereof
CN113003610B (en) * 2021-02-08 2023-09-15 华南协同创新研究院 Sodium ion battery anode material lithium manganate and preparation method and application thereof
CN114180635A (en) * 2021-10-28 2022-03-15 厦门理工学院 Single-crystal lithium manganate positive electrode material, preparation method and application
CN114105209A (en) * 2021-11-22 2022-03-01 江南大学 Doped modified lithium manganate lithium ion battery positive electrode material and preparation method thereof

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