CN105914363A - Lithium-rich layered cathode material of lithium ion battery, and preparation method and application of lithium-rich layered cathode material - Google Patents

Lithium-rich layered cathode material of lithium ion battery, and preparation method and application of lithium-rich layered cathode material Download PDF

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Publication number
CN105914363A
CN105914363A CN201610277798.3A CN201610277798A CN105914363A CN 105914363 A CN105914363 A CN 105914363A CN 201610277798 A CN201610277798 A CN 201610277798A CN 105914363 A CN105914363 A CN 105914363A
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lithium
preparation
cathode material
rich layered
layered cathode
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车仁超
武晶晶
刘夏林
宋元哲
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Fudan University
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Fudan University
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium-rich layered cathode material of a lithium ion battery, and a preparation method and an application of the lithium-rich layered cathode material. Octahedral oxide precursor is obtained by a mild and simple co-precipitation synthesis method, then the temperature is increased at the speed which is about 20-40 DEG C per minute by a microwave sintering method, and compared with the traditional muffle furnace sintering method by which the temperature is increased at the speed which is about 3 DEG C per minute, the preparation method has the feature that the structural orderness and the electrochemical performance are improved. The morphology and the size of the lithium-rich layered cathode material which is synthesized by the microwave sintering method are similar to those of precursor oxide, and compared with the same material which is obtained by sintering of the traditional muffle furnace, and is small in particle size and serious in agglomeration, the lithium-rich layered cathode material has the feature that the electrochemical performance is improved. The preparation steps are simple, the efficiency is high, and the preparation method is suitable for industrial scale-up to reduce energy consumption and reduce cost input. The preparation method which is used as a cathode material sintering method has extensive application value.

Description

A kind of lithium-rich anode material for lithium-ion batteries and its preparation method and application
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of anode material for lithium-ion batteries and its preparation method and application.
Background technology
Since Sony company in 1991 by LiCoO2Since rechargeable battery positive electrode, lithium ion battery just becomes the leading strength providing energy for consumer-elcetronics devices.After finding that graphite can be as ion cathode material lithium, positive electrode just becomes restriction battery performance and the principal element of cost, and therefore the preparation of positive electrode and chemical property become the hot issue of research field.In the last few years, there is the stratiform richness lithium material of the outstanding properties such as height ratio capacity, high stabilityxLi2MnO3∙(1-x)LiMO2(M= Ni, Mn, Co, Al, Zr ... single-element or combination) it is increasingly becoming study hotspot.Compare the most business-like LiCoO2, rich lithium material has the outstanding advantages such as low cost, hypotoxicity, height ratio capacity, is the strong candidate of a new generation's commercial li-ion cell positive material.Lithium ion battery belongs to secondary cell, relies primarily on lithium ion and reciprocated between a positive electrode and a negative electrode by electrolyte and realize during discharge and recharge, the most this interesting operation principle and be referred to as " rocking chair type battery " visually.The general expression of layer structure is LiMO2, for one or more combination in any in the elements such as Co, Ni, Mn, there is α-NaFeO2Layer structure,Crystal space group.Wherein M ion and Li ion are positioned at octahedral site, and lithium ion layer is between transition metal ions layer and oxonium ion layer.Comparing previous generation lithium battery and stoichiometric proportion layered cathode material, lithium-rich anode material chemical property in every respect has promoted, but is intended to widespread commercial and also has some shortcomings to overcome.Sintering process has conclusive impact to microstructure and the macro morphology of material, thus affects constant current charge-discharge performance and the chemical stability of battery material.Microwave sintering method is the most novel a kind of material preparation means, has the advantages such as the rate of heat addition fast, material is heated evenly, efficient energy-saving.And the characteristic changings such as the high rate of heat addition that it the brings crystal growing process of process of intercalation when preparing positive electrode.
Summary of the invention
It is an object of the invention to provide the anode material for lithium-ion batteries of a kind of electrochemical performance, and the presoma the inherited pattern of this anode material for lithium-ion batteries and the microwave sintering preparation method of size, and the application in lithium ion secondary battery electrode are provided.
The lithium ion cell positive nano material that the present invention provides, forxLi2MnO3∙(1-x)LiMO2M is Mn, Ni, Co, Al, Mg ... one, or several combinations, this materials'use different sintering processes, there is different granule-morphologies and size, the material using microwave sintering method to prepare maintains shape of octahedron and the granular size of oxidation of precursor thing substantially, uses the material of tradition Muffle furnace sintering preparation then to form the spherical particle that size is minimum, and it is serious to reunite.
The class octahedron nano material of the present invention has cycle performance and the high rate performance of excellence, and preparation efficiency is high, energy-conserving and environment-protective, can be made into new type lithium ion secondary cell extensive expanding production.
The present invention also provides for above-mentioned lithium ion cell positive nano materialxLi2MnO3∙(1-x)LiMO2Preparation method, concretely comprise the following steps:
(1) synthesis of oxidation of precursor thing, manganese sulfate and cobaltous sulfate that total concentration is 0.35-0.45 mole every liter are placed in beaker than for 2:1 according to the amount of material, the sodium hydroxide of 3.5-4.5 mole every liter and the ammonia of 0.03-0.05 mole every liter collectively as precipitant is instilled in beakers by (using calibrated shot instrument), simultaneously, insulation is stirred 8-10 hour at 55-65 degree Celsius, being precipitated thing, centrifugation also uses deionized water and ethanol solution to clean post-drying；
(2) lithium-rich materialxLi2MnO3∙(1-x)LiMO2Preparation, oxidation of precursor thing step (1) prepared is uniform with the Lithium hydrate mixed grinding of corresponding chemical metering ratio, it is placed in crucible, put in microwave Muffle furnace and be sintered, wherein, heating rate is 20-40 centigrade per minute, and sintering temperature is 700-900 degree Celsius, sintering time 0.1-1 hour, then naturally cools to room temperature.
The inventive method is simple, efficient, favorable repeatability.The lithium-rich material preparedxLi2MnO3∙(1-x)LiMO2 (M=Mn, Ni, Co, Al, Mg ...) compares the material of tradition Muffle furnace sintering preparation and has more preferable six side's degrees of order, structural intergrity.Microwave sintering method is used to prepare material, because it has the advantages that programming rate is fast, oxidation of precursor thing and Lithium hydrate can be made to carry out rapidly biphase embedding lithium react, avoid the occurrence of traditional slow and react the class molten salt reaction environment brought, so that presoma pattern and size are maintained, reduce ion mixing, prepare the material with more perfect cystal structure.Material is assembled into anode material for lithium-ion batteries, it is seen that compared the tradition material electrochemical performance prepared of Muffle furnace sintering process by microwave sintering method more preferable.
Accompanying drawing explanation
Fig. 1 isxLi2MnO3∙(1-x)LiMO2 (M=Mn, Ni, Co, Al, Mg ...) uses the scanning electron microscope image of nano material that microwave sintering method (a) and tradition Muffle furnace sintering process (b) are prepared respectively.
Fig. 2 isxLi2MnO3∙(1-x)LiMO2 (M=Mn, Ni, Co, Al, Mg ...) use the X-ray diffractogram of nano material that microwave sintering method (a) and tradition Muffle furnace sintering process (b) be prepared respectively, calculated the value of the c/a characterizing six side's degrees of order simultaneously, c/a is about big, characterizes material six side's degree of order the highest.
Fig. 3 isxLi2MnO3∙(1-x)LiMO2 (M=Mn, Ni, Co, Al, Mg ...) uses the circulation volume curve chart of nano material that microwave sintering method and tradition Muffle furnace sintering process are prepared respectively.Using the layered cathode material prepared of microwave sintering method 0.1C(20 milliampere every gram) capacity reaches as high as 280 MAH every gram under electric current, after 50 circles, capability retention is 98%, 1C(100 milliampere every gram) capacity the most still has 210 MAH every gram under electric current.The material comparing tradition Muffle furnace sintering has promoted.
Fig. 4 is the comparison of microwave sintering method of the present invention and conventional sintering method.
Detailed description of the invention
Following instance will the invention will be further described in conjunction with accompanying drawing.The present embodiment is implemented under premised on technical solution of the present invention, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiment.The experimental technique of unreceipted actual conditions in the following example, generally according to normal condition.
Embodiment 1
(1) synthesis of oxidation of precursor thing, manganese sulfate and cobaltous sulfate that total concentration is 0.4 mole every liter are placed in beaker than for 2:1 according to the amount of material, calibrated shot instrument is used to instill in beakers by the sodium hydroxide of 4 moles every liter and the ammonia of 0.04 mole every liter collectively as precipitant, simultaneously, insulation is at 60 degrees Celsius, stirring 8 hours, be precipitated thing, centrifugation also uses deionized water and ethanol solution to clean post-drying；
(2) lithium-rich material0.5Li2MnO3∙0.5LiCo0.67Mn0.33O2Preparation, oxidation of precursor thing step (1) prepared is uniform with the Lithium hydrate mixed grinding of corresponding chemical metering ratio, it is placed in crucible, put in microwave Muffle furnace and be sintered, heating rate is 35 centigrade per minutes, calcining heat is 900 degrees Celsius, and temperature retention time is 10 minutes, then naturally cools to room temperature；
(3) by step (2) product and Kynoar and conductive black with the proportional arrangement form slurry of 7:2:1, it is coated on Copper Foil, thickness 15 microns；
(4) pole piece to be applied is dried, and is cut into the circular pole piece of suitable size, with lithium metal as reference electrode, is assembled into button half-cell；
(5) on blue electricity battery test system, with electric current density 20 milliamperes every gram, the button cell that constant current charge-discharge testing procedure (4) assembles in the range of 2 ~ 4.8 volts.
Embodiment 2
(1) synthesis of oxidation of precursor thing, manganese sulfate and cobaltous sulfate that total concentration is 0.45 mole every liter are placed in beaker than for 2:1 according to the amount of material, calibrated shot instrument is used to instill in beakers by the sodium hydroxide of 4 moles every liter and the ammonia of 0.045 mole every liter collectively as precipitant, simultaneously, insulation is stirred 8 hours at 60 degrees Celsius, being precipitated thing, centrifugation also uses deionized water and ethanol solution to clean post-drying；
(2) lithium-rich material0.5Li2MnO3∙0.5LiCo0.67Mn0.33O2Preparation, oxidation of precursor thing step (1) prepared is uniform with the Lithium hydrate mixed grinding of corresponding chemical metering ratio, it is placed in crucible, put in tradition Muffle furnace and be sintered, heating rate is 3 centigrade per minutes, calcining heat is 700 degrees Celsius, and temperature retention time is 1 hour, then naturally cools to room temperature；
(3) by step (2) product and Kynoar and conductive black with the proportional arrangement form slurry of 7:2:1, it is coated on Copper Foil, thickness 15 microns；
(4) pole piece to be applied is dried, and is cut into the circular pole piece of suitable size, with lithium metal as reference electrode, is assembled into button half-cell；
(5) on blue electricity battery test system, with electric current density 20 milliamperes every gram, the button cell that constant current charge-discharge testing procedure (4) assembles in the range of 2 ~ 4.8 volts.
Use carbon nanotube composite materials prepared by the present invention in the range of 2 ~ 4.8 volts (with metal lithium electrodes as reference), under the electric current density of 20 milliamperes every gram, there is the reversible capacity of 260 ~ 280 MAH every gram.

Claims (3)

1. a preparation method for lithium-rich material, this material isxLi2MnO3∙(1-x)LiMO2, M is Mn, Ni, Co, Al, Mg ... one, or several combination, concretely comprising the following steps of preparation:
(1) synthesis of oxidation of precursor thing, manganese sulfate and cobaltous sulfate that total concentration is 0.35-0.45 mole every liter are placed in beaker than for 2:1 according to the amount of material, the sodium hydroxide of 3.5-4.5 mole every liter and the ammonia of 0.03-0.05 mole every liter collectively as precipitant is instilled in beakers, simultaneously, stir 8-10 hour under 55-65 degree Celsius, being precipitated thing, centrifugation also uses deionized water and ethanol solution to clean post-drying；
(2) lithium-rich materialxLi2MnO3∙(1-x)LiMO2Preparation, oxidation of precursor thing step (1) prepared is uniform with the Lithium hydrate mixed grinding of corresponding chemical metering ratio, it is placed in crucible, put in microwave Muffle furnace and be sintered, wherein heating rate is 20-40 centigrade per minute, sintering temperature is 700-900 degree Celsius, sintering time 0.1-1 hour, then naturally cools to room temperature.
2. the lithium-rich material obtained by preparation method described in claim 1.
3. the lithium-rich material that preparation method obtains as claimed in claim 1 is as the application of anode material for lithium-ion batteries.
CN201610277798.3A 2016-04-29 2016-04-29 Lithium-rich layered cathode material of lithium ion battery, and preparation method and application of lithium-rich layered cathode material Pending CN105914363A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
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CN106816601A (en) * 2017-01-14 2017-06-09 复旦大学 Lithium-rich manganese-based anode material and its preparation method and application
CN113194703A (en) * 2021-04-28 2021-07-30 复旦大学 Microwave absorption nano material with yolk shell structure and preparation and application thereof

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Patent Citations (2)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106816601A (en) * 2017-01-14 2017-06-09 复旦大学 Lithium-rich manganese-based anode material and its preparation method and application
CN113194703A (en) * 2021-04-28 2021-07-30 复旦大学 Microwave absorption nano material with yolk shell structure and preparation and application thereof
CN113194703B (en) * 2021-04-28 2022-05-31 复旦大学 Microwave absorption nano material with yolk shell structure and preparation and application thereof

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Application publication date: 20160831