CN1392621A - Method for preparing spherical positive pole active material for lithium ion position - Google Patents

Method for preparing spherical positive pole active material for lithium ion position Download PDF

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CN1392621A
CN1392621A CN02128853A CN02128853A CN1392621A CN 1392621 A CN1392621 A CN 1392621A CN 02128853 A CN02128853 A CN 02128853A CN 02128853 A CN02128853 A CN 02128853A CN 1392621 A CN1392621 A CN 1392621A
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active material
salt
lithium ion
lithium
positive pole
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CN1172387C (en
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杨岩峰
林志明
宋广智
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Technical Institute of Physics and Chemistry of CAS
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • C01G45/1242—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • C01G51/44—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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

This invention provides a method for preparing anode active material of spherical micron order powder for Li-ion battery including the following steps: firstly compounding soluble Co, Mn or Ni salts with LI salt in to a solution to be sprayed with inlet temperature at 300-450 deg.C, and outlet temperature at 200-305 deg.C and dried to form precursor powder, then decomposing in a thermo decomposition furnace at a controlled temperature of 850-1000 deg.c to be gathered by cyclone separation. The powder is calcinated again for 5-25 hours at 750-8000 deg.C under perturbation, and finally the spherical Li-ion battery anode active material is obtained.

Description

A kind of method for preparing spherical positive pole active material for lithium ion position
Technical field
The present invention relates to a kind of preparation method of anode active material of lithium ion battery, particularly relate to the preparation method who refers to a kind of spherical positive pole active material for lithium ion position.
Background technology
The development level of chemical power source has become the symbol of scientific and technological progress and modernized demand.The self-growth of current chemical power source has surpassed any one period in history.Volume is little, in light weight, capacity is big, power is high, pollution-free, long-life becomes the desirable demand of chemical cell.Lithium ion battery since have output voltage height, specific energy big, have extended cycle life, security performance is good, nuisanceless, the advantage of memory-less effect etc., so the design of new type lithium ion battery electrode material, research and development become the focus in material field.
What use was the most ripe in the present lithium ion battery active anode compartment material is cobalt acid lithium.A lithium of/2nd can reversibly be deviate from charge and discharge process and embedding again in the cobalt acid lithium, and its specific capacity is 140～150mAh/g.But people also are not content with existing lithium ion battery material, because lithium ion battery has only been brought into play the sub-fraction of lithium electrode specific energy.Improving the battery specific energy is that people constantly pursue.People wish that also battery has longer useful life in addition, can both normally use in the equator of sweltering heat, the cold arctic, and people wish that also the price of battery is more cheap.In order to reduce the battery material cost, reduce the consumption of cobalt resource, research emphasis is placed on lithium manganese compound and the nickel lithium compound.That begun practicability at present is spinel lithium manganate LiMn 2O 4, it is aboundresources, cheap not only, and because λ-MnO that battery generates when charging entirely 2Be difficult for decomposing, thus than cobalt acid lithium electrode safety, even can simplify or save battery protecting circuit, further reduce the battery cost.
At present, Chang Yong preparation method has high temperature solid-state method, low temperature synthetic technology.High temperature solid state reaction depends on the diffusion between the material.Because solid-state diffusion reaches the inhomogeneities of batch mixing more slowly, the reaction temperature of generally having relatively high expectations and longer reaction time, the preparation product exists than big difference on composition, structure, particle size distribution, causes the material electrochemical performance homogeneity wayward.The low temperature synthetic technology is to synthesize the homogeneous phase presoma by liquid-phase chemical reaction (as: precipitation reaction, solgel reaction, supercritical fluid drying etc.) or electrochemical reaction under the low temperature, and calcination process prepares positive electrode again.The low temperature synthetic technology can be prepared premium quality product, and especially the composition of product, pattern and microstructure can artificially be controlled.But the process of liquid phase method reaction at present reaches the demand that the requirement of equipment all is difficult to adapt to suitability for industrialized production, so the method for industrialization still adopts solid phase method.
In order to prepare more satisfactory active material, the spheric electrode active material is a bright spot of current people's research in the powder active material.Because usually the powder material of spheroidization has density height, feature capacious, and the spherical powder material has good fluidity, advantage that loading is big in the technology for preparing electrode process, and this is very favourable for preparation long-life, high-quality electrode.
About synthesizing of the active spherical cathode material of lithium ion battery, Chinese patent 98124404.1 (CN1218304A), Tsing-Hua University's journal (natural science edition) 2001, Vol.41, No.6,75-77 has successively synthesized spherical LiCoO respectively 2With spherical LiNi 0.8Co 0.2O 2, discharge capacity is respectively 137.9mAh/g and 172mAh/g.They are synthesizing spherical Co (OH) at first 2And spherical Ni 0.8Co 0.2(OH) 2, then with equimolar LiOHH 2O mixes through ball milling, places muffle furnace, 750 ℃～800 ℃ heat treatments 8 hours, obtains spherical LiCoO 2With spherical LiNi 0.8Co 0.2O 2This method is based on the Chemical Control crystallisation, and the reaction time is long.
Japanese patent laid-open 6-333562 discloses spherical LiCoO 2, average grain diameter 0.5～0.6 μ m, specific discharge capacity reaches 140mAh/g.But there is not concrete synthetic method.
United States Patent (USP) 5,958,362 adopt the liquid combustion technology, synthesize the positive electrode active materials of class sphere.In addition, Japanese Murata Manufacturing Co., Ltd. (US Patent 6,270,926, Lithium secondary battery) company adopts the atomizing pyrolytic technique to produce spherical lithium manganate.The porous offspring that this particle is made up of at the primary particle of 70～500nm particle diameter.Because primary particle has independently crystal, form the offspring of porous after, help the infiltration of nonaqueous electrolyte, increased contact area, thereby improved battery energy density, increased stability, shown the favorable charge-discharge performance.But this method gained particle size is directly at high temperature pyrolysis energy consumption height, uneconomical with solution at nanoscale.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method of micron-size spherical anode active material of lithium ion battery, by this method, realize the mixing of raw material on molecular level, in the short period of time, than synthetic uniform spherical anode active material of lithium ion battery under the low energy consumption.
The present invention realizes by following technical scheme:
The method for preparing spherical positive pole active material for lithium ion position provided by the invention divides three steps to carry out:
At first, make Co with solubility cobalt salt, manganese salt or nickel salt and solubility lithium salts wiring solution-forming 2+, Mn 2+Or Ni 2+With Li +Mole ratio be 1: 1; With this solution spray drying, 300 ℃～450 ℃ of inlet temperatures, 200 ℃～305 ℃ of outlet temperatures obtain the presoma powder;
Then this presoma powder is carried out thermal decomposition in thermal decomposition furnace, 850 ℃～1000 ℃ of control temperature, cyclonic separation is collected powder;
At last with this powder under 750 ℃～800 ℃, calcining again 5～25 hours under the disturbance, obtain spherical positive pole active material for lithium ion position.
The solubility cobalt salt is cobalt acetate or cobalt nitrate; Soluble manganese salt is manganese acetate or manganese nitrate; Soluble nickel salt is nickel acetate or nickel nitrate; The solubility lithium salts is lithium acetate or lithium nitrate.
The preparation of this method presoma, material rate can be regulated arbitrarily as required.
The spherical powder that method of the present invention is made can be used as anode active material of lithium ion battery.
Beneficial effect of the present invention is:
The present invention adopts low temperature softening to learn synthetic technology, and the advantage of comprehensive utilization low-temp reaction and spray pyrolysis adopts three-stage process, and the technology of preparing of preparation ball-shaped lithium-ion battery anode active material is provided.Present technique is carried out homogeneous reaction on the molecular level of solution, and its The Nomenclature Composition and Structure of Complexes is regulated and control, and makes that active substance of lithium ion battery anode homogenizes, densification, spheroidization.And the powder material of spheroidization has density height, feature capacious, and the spherical powder material has good fluidity, advantage that loading is big in the technology for preparing electrode process, so very favourable for preparation long-life, high-quality electrode.Method energy consumption of the present invention in addition is low, at the preparatory phase of presoma, adopts low temperature method to make presoma, has reduced energy consumption than direct pyrolysis.Because positive active material homogenizes, and makes the calcination reaction time shorten greatly.
Description of drawings
Fig. 1 is active substance of lithium ion battery anode LiCoO 2The X-ray diffraction spectrogram.
Fig. 2 is ball-shaped lithium-ion battery anode active material LiCoO 2The ESEM spectrogram.
Fig. 3 is irregular shape active substance of lithium ion battery anode LiCoO 2The ESEM spectrogram.
Embodiment
Embodiment 1
At first, make Co with cobalt acetate and lithium acetate wiring solution-forming 2+With Li +Mole ratio be 1: 1; With this solution spray drying, 300 ℃ of inlet temperatures, 200 ℃ of outlet temperatures obtain the presoma powder;
Then this presoma powder is carried out thermal decomposition in thermal decomposition furnace, 850 ℃ ± 5 ℃ of control temperature, cyclonic separation is collected powder;
At last with this powder under 800 ℃, calcining again 10 hours under the disturbance, obtain spherical positive pole active material for lithium ion position LiCoO 2Its X-ray diffraction spectrogram is seen accompanying drawing 1, and the ESEM spectrogram is seen accompanying drawing 2.
Embodiment 2
At first, make Co with cobalt acetate and lithium acetate wiring solution-forming 2+With Li +Mole ratio be 1: 1; With this solution spray drying, 430 ℃ of inlet temperatures, 200 ℃ of outlet temperatures obtain the presoma powder;
Then this presoma powder is carried out thermal decomposition in thermal decomposition furnace, 900 ℃ ± 5 ℃ of control temperature, cyclonic separation is collected powder;
At last with this powder under 800 ℃, calcining again 8 hours under the disturbance, obtain spherical positive pole active material for lithium ion position LiCoO 2
Embodiment 3
At first, make Co with cobalt nitrate and lithium nitrate wiring solution-forming 2+With Li +Mole ratio be 1: 1; With this solution spray drying, 350 ℃ of inlet temperatures, 200 ℃ of outlet temperatures obtain the presoma powder;
Then this presoma powder is carried out thermal decomposition in thermal decomposition furnace, 950 ℃ ± 5 ℃ of control temperature, cyclonic separation is collected powder;
At last with this powder under 800 ℃, calcining again 5 hours under the disturbance, obtain spherical positive pole active material for lithium ion position LiCoO 2
Embodiment 4
At first, make Co with cobalt acetate and lithium acetate wiring solution-forming 2+With Li +Mole ratio be 1: 1; With this solution spray drying, 430 ℃ of inlet temperatures, 300 ℃ of outlet temperatures obtain the presoma powder;
Then this presoma powder is carried out thermal decomposition in thermal decomposition furnace, 1000 ℃ ± 5 ℃ of control temperature, cyclonic separation is collected powder;
At last with this powder under 800 ℃, calcining again 10 hours under the disturbance, obtain spherical positive pole active material for lithium ion position LiCoO 2
Embodiment 5
At first, make Co with manganese acetate and lithium acetate wiring solution-forming 2+With Li +Mole ratio be 1: 1; With this solution spray drying, 350 ℃ of inlet temperatures, 200 ℃ of outlet temperatures obtain the presoma powder;
Then this presoma powder is carried out thermal decomposition in thermal decomposition furnace, 1000 ℃ ± 5 ℃ of control temperature, cyclonic separation is collected powder;
At last with this powder under 800 ℃, calcining again 24 hours under the disturbance, obtain spherical positive pole active material for lithium ion position LiMn 2O 4
Comparative examples
With cobalt acetate and lithium acetate wiring solution-forming, make Co 2+With Li +Mole ratio be 1: 1; With this solution spray drying, 430 ℃ of inlet temperatures, 300 ℃ of outlet temperatures obtain the presoma powder;
Then this presoma is placed directly in the muffle furnace and calcined 6 hours under 800 ℃, obtain anode active material of lithium ion battery LiCoO 2, but pattern is irregular shape, ESEM is seen accompanying drawing 3.

Claims (4)

1. method for preparing spherical positive pole active material for lithium ion position, it is characterized in that at first solubility cobalt salt, manganese salt or nickel salt and solubility lithium salts wiring solution-forming, with this solution spray drying, 300 ℃～450 ℃ of inlet temperatures, 200 ℃～305 ℃ of outlet temperatures obtain the presoma powder;
Then this presoma powder is carried out thermal decomposition in thermal decomposition furnace, 850 ℃～1000 ℃ of control temperature, cyclonic separation is collected powder;
At last with this powder under 750 ℃～800 ℃, calcining again 5～25 hours under the disturbance, obtain spherical positive pole active material for lithium ion position.
2. the described method for preparing spherical positive pole active material for lithium ion position of claim 1 is characterized in that at first with solubility cobalt salt, manganese salt or nickel salt and solubility lithium salts wiring solution-forming, Co 2+, Mn 2+Or Ni 2+With Li +Mole ratio can regulate arbitrarily.
3. claim 1 or the 2 described methods that prepare spherical positive pole active material for lithium ion position is characterized in that at first solubility cobalt salt, manganese salt or nickel salt and solubility lithium salts wiring solution-forming are made Co 2+, Mn 2+Or Ni 2+With Li +Mole ratio be 1: 1.
4. the described method for preparing spherical positive pole active material for lithium ion position of claim 1 is characterized in that described solubility cobalt salt is cobalt acetate or cobalt nitrate; Soluble manganese salt is manganese acetate or manganese nitrate; Soluble nickel salt is nickel acetate or nickel nitrate; The solubility lithium salts is lithium acetate or lithium nitrate.
CNB021288534A 2002-08-16 2002-08-16 Method for preparing spherical positive pole active material for lithium ion position Expired - Fee Related CN1172387C (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1319865C (en) * 2006-02-24 2007-06-06 长沙矿冶研究院 LiCoO for preparing lithium ion battery anode material2Method (2)
CN100342569C (en) * 2005-07-15 2007-10-10 广州鸿森材料有限公司 Method for synthesizing lithium ion cell positive cell polar material rotary furnace
CN100423328C (en) * 2005-01-14 2008-10-01 哈尔滨光宇电源股份有限公司 Preparation method of positive electrode material of lithium ion secondary cell
CN102237516A (en) * 2010-04-21 2011-11-09 中国科学院宁波材料技术与工程研究所 Preparation method of lithium ion power battery positive electrode material
CN102357308A (en) * 2011-10-19 2012-02-22 江西稀有稀土金属钨业集团有限公司 Method for directly preparing anhydrous cobalt chloride powder from cobalt chloride solution
CN102655230A (en) * 2011-03-03 2012-09-05 苏州大学 Cathode material for lithium ion secondary battery, preparation method of cathode material, lithium ion secondary battery anode and lithium ion secondary battery
CN102906023A (en) * 2010-06-25 2013-01-30 赢创德固赛有限公司 Method for producing mixed oxides comprising lithium
CN102983326A (en) * 2012-09-20 2013-03-20 横店集团东磁股份有限公司 Spherical lithium-nickel-cobalt composite oxide positive electrode material preparation method
CN106946296A (en) * 2017-03-03 2017-07-14 中南大学 A kind of micron order monocrystalline lithium nickelate and its preparation method and application
CN107585794A (en) * 2017-09-13 2018-01-16 中南大学 Tertiary cathode material, its presoma and the preparation method of the material and presoma
CN110085845A (en) * 2019-05-13 2019-08-02 中南大学 A kind of nickel-base anode material and preparation method thereof with core-shell structure

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100423328C (en) * 2005-01-14 2008-10-01 哈尔滨光宇电源股份有限公司 Preparation method of positive electrode material of lithium ion secondary cell
CN100342569C (en) * 2005-07-15 2007-10-10 广州鸿森材料有限公司 Method for synthesizing lithium ion cell positive cell polar material rotary furnace
CN1319865C (en) * 2006-02-24 2007-06-06 长沙矿冶研究院 LiCoO for preparing lithium ion battery anode material2Method (2)
CN102237516A (en) * 2010-04-21 2011-11-09 中国科学院宁波材料技术与工程研究所 Preparation method of lithium ion power battery positive electrode material
CN102237516B (en) * 2010-04-21 2014-07-23 中国科学院宁波材料技术与工程研究所 Preparation method of lithium ion power battery positive electrode material
CN102906023B (en) * 2010-06-25 2015-04-01 赢创德固赛有限公司 Method for producing mixed oxides comprising lithium
CN102906023A (en) * 2010-06-25 2013-01-30 赢创德固赛有限公司 Method for producing mixed oxides comprising lithium
CN102655230A (en) * 2011-03-03 2012-09-05 苏州大学 Cathode material for lithium ion secondary battery, preparation method of cathode material, lithium ion secondary battery anode and lithium ion secondary battery
CN102655230B (en) * 2011-03-03 2015-11-25 苏州大学 For the positive electrode and preparation method thereof of lithium rechargeable battery, lithium ion secondary battery positive electrode and lithium rechargeable battery
CN102357308A (en) * 2011-10-19 2012-02-22 江西稀有稀土金属钨业集团有限公司 Method for directly preparing anhydrous cobalt chloride powder from cobalt chloride solution
CN102983326B (en) * 2012-09-20 2015-04-29 横店集团东磁股份有限公司 Spherical lithium-nickel-cobalt composite oxide positive electrode material preparation method
CN102983326A (en) * 2012-09-20 2013-03-20 横店集团东磁股份有限公司 Spherical lithium-nickel-cobalt composite oxide positive electrode material preparation method
CN106946296A (en) * 2017-03-03 2017-07-14 中南大学 A kind of micron order monocrystalline lithium nickelate and its preparation method and application
CN106946296B (en) * 2017-03-03 2019-01-25 中南大学 A kind of micron order monocrystalline lithium nickelate and its preparation method and application
CN107585794A (en) * 2017-09-13 2018-01-16 中南大学 Tertiary cathode material, its presoma and the preparation method of the material and presoma
CN107585794B (en) * 2017-09-13 2019-05-14 中南大学 The preparation method of tertiary cathode material and the material and its presoma
CN110085845A (en) * 2019-05-13 2019-08-02 中南大学 A kind of nickel-base anode material and preparation method thereof with core-shell structure

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