CN103956478A - Preparation method of high-specific-capacity lithium-rich anode material - Google Patents

Preparation method of high-specific-capacity lithium-rich anode material Download PDF

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Publication number
CN103956478A
CN103956478A CN201410190666.8A CN201410190666A CN103956478A CN 103956478 A CN103956478 A CN 103956478A CN 201410190666 A CN201410190666 A CN 201410190666A CN 103956478 A CN103956478 A CN 103956478A
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acetate
lithium
preparation
rich
anode material
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严乙铭
邓晨
刘明龙
甄树瑜
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Beijing Institute of Technology BIT
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Beijing Institute of Technology BIT
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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
    • 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
    • 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 high-specific-capacity lithium-rich anode material, belongs to the field of chemical power source material preparation and lithium ion battery anode materials. The preparation method comprises the following steps of dissolving manganese acetate, nickel acetate, cobaltous acetate and lithium acetate in a solvent, stirring the manganese acetate, the nickel acetate, the cobaltous acetate and the lithium acetate so as to obtain an acetate solution which is uniformly mixed, carrying out magnetic stirring and evaporating under heating of a water bath until a mixing liquid is thick colloid, and placing the mixing liquid in a drying box to dry so as to obtain precursor powder; warming the dried precursor powder to calcine twice, and reducing to room temperature by adopting a furnace cooling manner so as to obtain a multi-element lithium-rich material Li1.2Mn0.54Ni0.13 Co0.13O2. A material prepared by the preparation method provided by the invention is high in bulk phase crystallinity, the grain diameter of a material is small, the distribution is uniform, a transition metal element proportion approaches to a theoretical value, a synthesis step is simple, the material is easy for mass production, synthesizing nondeterminacy factors in a process are less, the characteristics give the high specific capacity and the cycling stability for the material, and an electrochemical property of the material is excellent.

Description

A kind of preparation method of height ratio capacity lithium-rich anode material
Technical field
The present invention relates to a kind of preparation method of height ratio capacity lithium-rich anode material, belong to the preparation of chemical power source material and anode material for lithium-ion batteries field.
Background technology
Along with scientific and technological development, increase day by day to the requirement of energy storage device in the fields such as electronic product, space industry, electric automobile, tend to gradually the future development that energy density is high, volume is little, have extended cycle life, lithium ion battery is widely applied because it meets These characteristics.Lithium ion battery forms and mainly to comprise positive and negative pole material, barrier film, electrolyte etc., and in all material forms, positive electrode is in occupation of core position, and it directly affects the important performances such as cost, capacity, cycle life, safety of battery.
The anode material for lithium-ion batteries of exploitation comprises cobalt acid lithium, lithium nickelate, LiMn2O4, nickel manganese/cobalt binary and the ternary material of stratiform, the LiMn2O4 (LiMn of spinel structure at present 2o 4) and 5V high pressure LiNi 0.5mn 0.5o 4, olivine-type structure LiFePO4, and the xLi of layed solid-solution structure 2mnO 3(1-x) LiMO 2the rich lithium material of (0<x<1, M=Ni, Co, Mn) manganese base.The specific capacity of front several electrode materials is all below 200mAh/g, only have rich lithium material to be greater than 200mAh/g, with respect to specific capacity more than carbon back negative pole 350mAh/g, the specific capacity of positive electrode is in urgent need to be improved, so the height ratio capacity feature of rich lithium material becomes the preferred material of commercialization anode of future generation.
With other positive electrodes, compare, manganese base lithium-rich anode material obtains extensive concern because of it compared with high specific capacity.The rich lithium material Li being made by alcoholysis solid phase method 1.17mn 0.5ni 0.17co 0.17o 2(publication No. CN103066264A), although the even specific discharge capacity of particle diameter still has much room for improvement, the specific discharge capacity after a few circulations is still lower.In lithium-rich anode series material, stratiform Li 1.2mn 0.54ni 0.13co 0.13o 2material obtains broad research because of its height ratio capacity and good cycle performance.But some problems of rich lithium material itself are restricting its development and application, as poor in heavy-current discharge performance, synthetic method is complicated, influenced many factors etc.
Summary of the invention
The object of the invention is, for, complicated process of preparation unstable for existing stratiform lithium-rich anode material cycle performance and the low problem of specific discharge capacity, provides a kind of preparation method of height ratio capacity lithium-rich anode material.Positive electrode body phase degree of crystallinity prepared by this method is high, and material particle size is less and be evenly distributed, and transition metal ratio approaches theoretical value, and these features are given material height ratio capacity and cyclical stability.
The present invention realizes by following concrete technical scheme.
A preparation method for height ratio capacity lithium-rich anode material, concrete steps are as follows:
Step 1, manganese acetate, nickel acetate, cobalt acetate and lithium acetate are dissolved in solvent, stir the acetate solution that obtains mixing; Manganese acetate, nickel acetate, cobalt acetate and lithium acetate mixing molar ratio are 0.54:0.13:0.13:1.2～1.3;
Step 2, the acetate solution of step 1 gained is heated under 60～80 ℃ of water-baths, electromagnetic agitation is evaporated to acetate solution, and to present aubergine thick; Then be positioned at 80～120 ℃ of temperature and be dried, grind, obtain precursor powder;
Step 3, the precursor powder of step 2 gained is calcined; Heating rate with 2～5 ℃/min rises to 450～600 ℃ from room temperature, and temperature retention time is 4～8h; Naturally cool to room temperature, after grinding, with 2～5 ℃/min heating rate, heat up, from room temperature, rise to calcining 800 ℃～950 ℃, temperature retention time is 8～12h; Cool to room temperature with the furnace, through grinding, obtain brown rich lithium material Li 1.2mn 0.54ni 0.13co 0.13o 2;
Described solvent is absolute ethyl alcohol or deionized water.
Beneficial effect
1, the preparation method of a kind of height ratio capacity lithium-rich anode material of the present invention, because adopt acetate one-step synthesis target product, raw material only has corresponding acetate, do not introduce fuse salt and other ions, and through stirring in water bath, make metallic element reach the mixability of molecular level, the material element of preparation is evenly distributed.
2, the preparation method of a kind of height ratio capacity lithium-rich anode material of the present invention, because prepared material bodies phase degree of crystallinity is high, particle diameter is less and be evenly distributed, specific area is large, fully contact with electrolyte, reaction site is many, is beneficial to deviating from and embedding of lithium ion, make the cycle performance of battery of material assembling stable, specific discharge capacity maximum reaches 316.5mAh/g.
3, the preparation method of a kind of height ratio capacity lithium-rich anode material of the present invention, because synthesis step is simple, good process repeatability, transition metal ratio approaches theoretical value, be easy to produce in enormous quantities, in building-up process, uncertain factor is few, and the fluctuation of product physical and chemical performance is little, and the chemical property of material is excellent.
Accompanying drawing explanation
The lithium-rich anode material Li that Fig. 1 adopts the inventive method to prepare 1.2mn 0.54ni 0.13co 0.13o 2xRD diffracting spectrum;
The lithium-rich anode material Li that Fig. 2 adopts the inventive method to prepare 1.2mn 0.54ni 0.13co 0.13o 2stereoscan photograph;
The lithium-rich anode material Li that Fig. 3 adopts the inventive method to prepare 1.2mn 0.54ni 0.13co 0.13o 2first charge-discharge curve;
The lithium-rich anode material Li that Fig. 4 adopts the inventive method to prepare 1.2mn 0.54ni 0.13co 0.13o 2cyclic curve.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the present invention will be further described.
Embodiment 1
A kind of preparation method of high power capacity lithium-rich anode material, by manganese acetate, nickel acetate, cobalt acetate and lithium acetate by stoichiometric proportion 0.54:0.13:0.13:1.26 (because of elemental lithium calcination process volatile, want excessive 5%) be dissolved in ethanol, stir the acetate solution that obtains mixing.By this solution, under 80 ℃ of heating water baths, electromagnetic agitation is evaporated to mixed liquor and presents the thick colloid of aubergine, places dry 12h in 80 ℃ of drying boxes, obtains precursor powder.Dried mixture is ground to form to powdery, be placed in the calcining that heats up of high temperature furnace Program, with the heating rate of 5 ℃/min, rise to 500 ℃, temperature retention time is 5h.After cool drying grinds, with 5 ℃/min heating rate, heat up, calcining at 850 ℃, temperature retention time is 10h.After sintering finishes, take to be down to room temperature with the cooling mode of stove, through grinding, obtain brown rich lithium material Li 1.2mn 0.54ni 0.13co 0.13o 2.
As shown in Figure 1, the diffraction maximum of material is α-NaFeO 2stratiform configuration characteristic peak, belong to hexagonal crystal system.Diffraction maximum between 20 °-25 ° is not the characteristic peak of R-3m structure, and their correspondences the Li existing in material 2mnO 3the LiMn in structure nano region (nano-domains) 6cation superlattice ordered arrangement, can be attributed to space group is the monocline cell configuration of C2/m, diffraction maximum is herein to weigh in material to have or not Li 2mnO 3the characteristic peak of composition.In XRD collection of illustrative plates, the bimodal and bimodal obvious division in (018)/(110) in (006)/(012), indicates that material has good layer structure.And I (003)/ I (104)peak intensity ratio be greater than 1.2, show that the degree of material intermediate ion mixing is less.Therefore the Li preparing 1.2mn 0.54ni 0.13co 0.13o 2material has good layer structure and crystal structure degree.
Fig. 2 is this lithium-rich anode material Li 1.2mn 0.54ni 0.13co 0.13o 2stereoscan photograph.In figure, the grain diameter of display material is between 120～300nm, and particle size distribution range is narrower, and size evenly, does not have obvious agglomeration, and particle surface is more smooth.
Fig. 3 is this lithium-rich anode material Li 1.2mn 0.54ni 0.13co 0.13o 2first charge-discharge curve.Battery carries out charge-discharge test under 0.1C, and first discharge specific capacity reaches 294.1mAh/g.
Fig. 4 is this lithium-rich anode material Li 1.2mn 0.54ni 0.13co 0.13o 2100 circle cyclic curves.When the 10th circle, the specific discharge capacity of material rises to maximum 316.5mAh/g.After experience 100 circle charge and discharge cycles tests, the specific discharge capacity of material is 228.2mAh/g, and capability retention is 72.1%.
Embodiment 2
A preparation method for height ratio capacity lithium-rich anode material, is dissolved in manganese acetate, nickel acetate, cobalt acetate and lithium acetate in deionized water by stoichiometric proportion 0.54:0.13:0.13:1.26, stirs the acetate solution that obtains mixing.By this solution, under 80 ℃ of heating water baths, electromagnetic agitation is evaporated to mixed liquor and presents the thick colloid of aubergine, places dry 12h in 80 ℃ of drying boxes, obtains precursor powder.Dried mixture is ground to form to powdery, be placed in the calcining that heats up of high temperature furnace Program, with the heating rate of 5 ℃/min, rise to 500 ℃, temperature retention time is 5h.After cool drying grinds, with 5 ℃/min heating rate, heat up, calcining at 850 ℃, temperature retention time is 10h.After sintering finishes, take to be down to room temperature with the cooling mode of stove, through grinding, obtain brown rich lithium material Li 1.2mn 0.54ni 0.13co 0.13o 2.
After positive electrode packaged battery, the maximum specific discharge capacity of gained is 272.2mAh/g, and after hundred circles, capability retention is 71.9%.
Embodiment 3
A preparation method for height ratio capacity lithium-rich anode material, is dissolved in manganese acetate, nickel acetate, cobalt acetate and lithium acetate in ethanol by stoichiometric proportion 0.54:0.13:0.13:1.26, stirs the acetate solution that obtains mixing.By this solution, under 80 ℃ of heating water baths, electromagnetic agitation is evaporated to mixed liquor, and to present aubergine thick, places dry 12h in 80 ℃ of drying boxes, obtains precursor powder.Dried mixture is ground to form to powdery, be placed in the calcining that heats up of high temperature furnace Program, with the heating rate of 5 ℃/min, rise to 500 ℃, temperature retention time is 5h.After cool drying grinds, with 5 ℃/min heating rate, heat up, calcining at 900 ℃, temperature retention time is 10h.After sintering finishes, take to be down to room temperature with the cooling mode of stove, through grinding, obtain brown rich lithium material Li 1.2mn 0.54ni 0.13co 0.13o 2.
After positive electrode packaged battery, the maximum specific discharge capacity of gained is 244mAh/g, and after hundred circles, capability retention is 70%.

Claims (2)

1. a preparation method for height ratio capacity lithium-rich anode material, is characterized in that: concrete steps are as follows:
Step 1, manganese acetate, nickel acetate, cobalt acetate and lithium acetate are dissolved in solvent, stir the acetate solution that obtains mixing; Manganese acetate, nickel acetate, cobalt acetate and lithium acetate mixing molar ratio are 0.54:0.13:0.13:1.2～1.3;
Step 2, the acetate solution of step 1 gained is heated under 60～80 ℃ of water-baths, electromagnetic agitation is evaporated to acetate solution and presents thick colloid; Then be positioned at 80～120 ℃ of temperature and be dried, grind, obtain precursor powder;
Step 3, the precursor powder of step 2 gained is calcined; Heating rate with 2～5 ℃/min rises to 450～600 ℃ from room temperature, and temperature retention time is 4～8h; Naturally cool to room temperature, after grinding, with 2～5 ℃/min heating rate, heat up, from room temperature, rise to calcining 800 ℃～950 ℃, temperature retention time is 8～12h; Cool to room temperature with the furnace, through grinding, obtain polynary rich lithium material Li 1.2mn 0.54ni 0.13co 0.13o 2.
2. the preparation method of a kind of height ratio capacity lithium-rich anode material as claimed in claim 1, is characterized in that: described solvent is absolute ethyl alcohol or deionized water.
CN201410190666.8A 2014-05-07 2014-05-07 Preparation method of high-specific-capacity lithium-rich anode material Pending CN103956478A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104966820A (en) * 2015-05-08 2015-10-07 广州锂宝新材料有限公司 Lithium-ion battery precursor material, composite positive electrode material and preparation method thereof
CN108123131A (en) * 2016-11-28 2018-06-05 中国科学院大连化学物理研究所 A kind of preparation method of lithium ion battery ternary nano monocrystalline positive electrode
WO2018121100A1 (en) * 2016-12-30 2018-07-05 徐茂龙 Method for preparing power-type and high-capacity modified nca anode material
CN108493446A (en) * 2018-04-24 2018-09-04 中国矿业大学 A kind of preparation method of lithium ion battery lithium-rich manganese base material
WO2019080310A1 (en) * 2017-10-23 2019-05-02 广东工业大学 Molybdenum-doped lithium-rich manganese-based cathode material and preparation method therefor
CN112680791A (en) * 2020-12-09 2021-04-20 北京理工大学重庆创新中心 Single crystal type IV-VI-VIII group lithium-rich disordered rock salt structure cathode material and preparation method thereof
CN114649524A (en) * 2020-12-18 2022-06-21 恒大新能源技术(深圳)有限公司 High-nickel positive electrode material, preparation method thereof and lithium battery
CN114695874A (en) * 2022-04-11 2022-07-01 中山大学 Synthesis method of O2 type lithium-rich manganese-based cathode material with low voltage hysteresis
CN114843495A (en) * 2022-05-26 2022-08-02 临沂大学 Lithium-defect high-nickel lithium-rich layered material and preparation method thereof

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104966820A (en) * 2015-05-08 2015-10-07 广州锂宝新材料有限公司 Lithium-ion battery precursor material, composite positive electrode material and preparation method thereof
CN108123131A (en) * 2016-11-28 2018-06-05 中国科学院大连化学物理研究所 A kind of preparation method of lithium ion battery ternary nano monocrystalline positive electrode
CN108123131B (en) * 2016-11-28 2021-03-09 中国科学院大连化学物理研究所 Preparation method of ternary nano single crystal cathode material of lithium ion battery
WO2018121100A1 (en) * 2016-12-30 2018-07-05 徐茂龙 Method for preparing power-type and high-capacity modified nca anode material
WO2019080310A1 (en) * 2017-10-23 2019-05-02 广东工业大学 Molybdenum-doped lithium-rich manganese-based cathode material and preparation method therefor
CN108493446A (en) * 2018-04-24 2018-09-04 中国矿业大学 A kind of preparation method of lithium ion battery lithium-rich manganese base material
CN112680791A (en) * 2020-12-09 2021-04-20 北京理工大学重庆创新中心 Single crystal type IV-VI-VIII group lithium-rich disordered rock salt structure cathode material and preparation method thereof
CN114649524A (en) * 2020-12-18 2022-06-21 恒大新能源技术(深圳)有限公司 High-nickel positive electrode material, preparation method thereof and lithium battery
CN114695874A (en) * 2022-04-11 2022-07-01 中山大学 Synthesis method of O2 type lithium-rich manganese-based cathode material with low voltage hysteresis
CN114843495A (en) * 2022-05-26 2022-08-02 临沂大学 Lithium-defect high-nickel lithium-rich layered material and preparation method thereof

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Application publication date: 20140730