CN111326730A - Surface layer gradient doped lithium-rich layered oxide cathode material and preparation method and application thereof - Google Patents

Surface layer gradient doped lithium-rich layered oxide cathode material and preparation method and application thereof Download PDF

Info

Publication number
CN111326730A
CN111326730A CN201911417710.3A CN201911417710A CN111326730A CN 111326730 A CN111326730 A CN 111326730A CN 201911417710 A CN201911417710 A CN 201911417710A CN 111326730 A CN111326730 A CN 111326730A
Authority
CN
China
Prior art keywords
lithium
layered oxide
rich layered
powder
oxide cathode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201911417710.3A
Other languages
Chinese (zh)
Inventor
罗冬
谢惠娴
林展
梁子扬
崔佳祥
丁晓凯
任晴晴
张祖豪
张博阳
谭富林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangdong University of Technology
Original Assignee
Guangdong University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangdong University of Technology filed Critical Guangdong University of Technology
Priority to CN201911417710.3A priority Critical patent/CN111326730A/en
Publication of CN111326730A publication Critical patent/CN111326730A/en
Pending legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00Compounds of nickel
    • C01G53/40Nickelates
    • C01G53/42Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/30Particle morphology extending in three dimensions
    • C01P2004/32Spheres
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/61Micrometer sized, i.e. from 1-100 micrometer
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/40Electric properties
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention belongs to the technical field of lithium ion batteries, and discloses a surface layer gradient doped lithium-rich layered oxide cathode material, and a preparation method and application thereof. The chemical formula of the material is Li1.2‑ xMn0.6Ni0.2MxO2M is Mg, Al, Zn, Y, Li or Ce, 0<x<0.1. The preparation method comprises the steps of adding nitrate into a precursor of the transition metal, and pretreating the precursor in a box furnace or an oven at 100-400 DEG CAnd mixing the obtained powder with lithium salt and molten salt, performing heat treatment at 700-1000 ℃, washing with water, drying, and then performing calcination at 300-600 ℃ to obtain the lithium ion secondary battery. The surface layer gradient doped lithium-rich layered oxide cathode material has slower capacity attenuation and better rate capability. When the voltage window is 2-4.8V and the current density is 200mA/g, the capacity retention rate of the material is 90% after 250 times of charging and discharging.

Description

Surface layer gradient doped lithium-rich layered oxide cathode material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a surface layer gradient doped lithium-rich layered oxide cathode material, and a preparation method and application thereof.
Background
The lithium ion battery has the advantages of long service life, large specific energy, high charging and discharging efficiency, high safety performance and the like, and is widely applied to the fields of mobile phones, portable computers, cameras and the like. The core technology of lithium ion battery production is the anode material, and the lithium-rich layered material has become the next generation of lithium ion battery candidate anode material. At present, one of the major problems of lithium-rich layered oxides is poor cycling stability and short lifetime, thus severely hampering their commercial application.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the primary object of the present invention is to provide a surface layer gradient doped lithium-rich layered oxide cathode material.
The invention also aims to provide a preparation method of the surface layer gradient doped lithium-rich layered oxide cathode material. The method is mainly used for the commercialized Mn0.75Ni0.25CO3Or Mn0.75Ni0.25(OH)2The precursor is subjected to simple nitrate pretreatment, the surface of the precursor is uniformly coated with oxides, and then the precursor is calcined at high temperature by a molten salt method, and trace and uniform doping of elements is carried out on the surface of the material. The processing method successfully modifies the surface of the lithium-rich layered oxide material, so that the material structure is more stable, and the stability of the battery in the long-cycle process is maintained; meanwhile, the oxide coated on the surface avoids the exposure of active substances of the material, reduces the structural damage caused by side reaction with electrolyte and inhibits the increase of electrochemical resistance. The preparation method overcomes the defects of fast capacity attenuation and poor cycle stability of the lithium-rich layered oxide material, and the treatment process has the advantages of simple process, easy control, good repeatability and the like, thereby having great commercial prospect.
The invention further aims to provide application of the surface layer gradient doped lithium-rich layered oxide cathode material.
The purpose of the invention is realized by the following technical scheme:
a surface layer gradient doped lithium-rich layered oxide cathode material has a chemical formula of Li1.2- xMn0.6Ni0.2MxO2M is Mg, Al, Zn, Y, Li or Ce, 0<x<0.1。
The preparation method of the surface layer gradient doped lithium-rich layered oxide cathode material comprises the following operation steps:
mixing a carbonate precursor of transition metal with nitrate, and carrying out pretreatment at 100-400 ℃ in a box furnace or an oven; after the reaction is finished, washing with water to remove impurities, and drying; uniformly mixing the dried precursor A with lithium salt and molten salt, carrying out heat treatment at 700-1000 ℃, and cooling along with the furnace after the reaction is finished; washing the obtained sample with water to remove impurities, and drying to obtain powder; and (3) the powder is sintered at the temperature of 300-600 ℃, and then the surface layer gradient doped lithium-rich layered oxide anode material is prepared.
Preferably, the carbonate precursor of the transition metal is Mn0.75Ni0.25CO3Or Mn0.75Ni0.25(OH)2(ii) a The nitrate is M (NO)3)yM is Mg, Al, Zn, Y, Li or Ce.
Preferably, the lithium salt is one or more of lithium acetate, lithium carbonate and lithium hydroxide.
Preferably, the molten salt is sodium chloride and potassium chloride.
Preferably, the molar ratio of the carbonate precursor of the transition metal to the lithium salt is 1: (1-1.1); the molar ratio of the molten salt to the sum of the carbonate precursor and the lithium salt of the transition metal is 4: 1.
preferably, the pretreatment time is 12-24 h.
Preferably, the time of the heat treatment is 8-16 h.
Preferably, the time of the burn-back is 3-5 h.
The surface layer gradient doped lithium-rich layered oxide cathode material is applied to the field of lithium ion batteries.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the surface layer gradient doped lithium-rich layered oxide cathode material overcomes the defect of poor cycling stability of the previous material. When the voltage window is 2.0-4.8V and the current density is 200mA/g, the highest capacity of the anode material can reach 229mAh/g, the capacity retention rate after 250 cycles is as high as 90%, and the capacity retention rate still has 79% even after 400 cycles.
(2) The invention first attempts to add nitrate to the precursor, first forms a uniform thin oxide layer, and then performs uniform doping of elements under high temperature calcination conditions. The oxide coated on the surface avoids the exposure of active substances of the material, reduces the structural damage caused by side reaction with electrolyte and inhibits the increase of electrochemical resistance. The doped elements stabilize the structure of the material and avoid the distortion of the whole structure in the process of lithium ion deintercalation. Under the dual action, the effect of inhibiting capacity fading is achieved, so that the material shows excellent cycling stability.
(3) The method for pretreating the precursor by using the nitrate for the surface gradient lithium-rich layered oxide-doped anode material uniformly dopes chemical elements, improves the structural stability, improves the ionic conductivity and ensures that the material has excellent rate performance.
Drawings
FIG. 1 shows Li in example 11.19Mn0.6Ni0.2Al0.01O2X-ray diffraction pattern of the powder.
FIG. 2 shows Li in example 11.19Mn0.6Ni0.2Al0.01O2SEM photograph of the powder.
FIG. 3 shows a schematic view of a catalyst system using Li of example 11.19Mn0.6Ni0.2Al0.01O2The powder is used as a positive electrode and 200mAg at room temperature-1First charge and discharge curve.
FIG. 4 shows a schematic view of a Li alloy obtained by using Li of example 11.19Mn0.6Ni0.2Al0.01O2The powder is used as a positive electrode and 200mAg at room temperature-1Time capacity stability curve.
FIG. 5 shows a schematic view of a Li alloy of example 11.19Mn0.6Ni0.2Al0.01O2The powder is used as a rate performance curve of the anode at room temperature.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. The reagents, methods and apparatus employed in the present invention are conventional in the art, unless otherwise specified.
Example 1: surface layer gradient doped lithium-rich layered oxide cathode material Li1.19Mn0.6Ni0.2Al0.01O2Preparation of
(1) 0.9270g of a transition metal carbonate precursor (Mn) was weighed out0.75Ni0.25CO3) 0.1020g of Al (NO) were added3)3·9H2O, fully and uniformly mixing, putting into a crucible, and reacting in a box-type furnace at 350 ℃ for 12h, filtering and drying after the reaction is finished to prepare a treated precursor A;
(2) precursor A was mixed with 0.4655g of lithium salt (Li)2CO3) Mixing, adding 4g of sodium chloride and 2g of potassium chloride, fully grinding, filling into a crucible, reacting for 12 hours at 850 ℃ in a box-type furnace, cooling along with the furnace, washing with water and drying to obtain powder;
(3) grinding the powder, putting the powder into a crucible, reacting for 3 hours in a box-type furnace at 400 ℃, and cooling along with the furnace to obtain Li1.19Mn0.6Ni0.2Al0.01O2The powder is the surface layer gradient doped lithium-rich layered oxide anode material.
FIG. 1 shows Li in this example1.19Mn0.6Ni0.2Al0.01O2X-ray diffraction pattern of the powder. As can be seen from FIG. 1, the synthesized powder is O3Type of lithium-rich oxide is Li2MnO3And mixed phases of ternary layered materials. FIG. 2 shows Li in this example1.19Mn0.6Ni0.2Al0.01O2SEM photograph of the powder. As can be seen from fig. 2, the synthesized positive electrode material powder was assembled microspheres.
The Li prepared by adopting a button cell is tested1.19Mn0.6Ni0.2Al0.01O2Preparing the powder, conductive carbon black and a binder polyvinylidene fluoride (PVDF) into an electrode according to the mass ratio of 8:1:1, taking a metal lithium sheet as a counter electrode, and 1 mol.L-1LiPF6The volume ratio of EC, DMC and EMC is 1:1:1, the electrolyte is used as the material of the/EC, DMC and EMC is used as the material of the diaphragm, the battery test system is LAND, the charge-discharge voltage window is 2.0-4.8V, and the charge-discharge current density is respectively 200mAg-1The material shows good electrochemical performance when being used as the anode of a lithium ion battery. FIG. 3 shows Li in the present example1.19Mn0.6Ni0.2Al0.01O2The powder is used as a positive electrode and has a volume of 200mAg at room temperature-1First charge and discharge curve. From FIG. 3, it can be seen that at 200mAg-1The first discharge specific capacity of the lithium ion battery is 229mAhg under the charge-discharge current density-1(ii) a FIG. 4 shows a schematic view of a Li alloy obtained by using Li of example 11.19Mn0.6Ni0.2Al0.01O2The powder is used as a positive electrode and 200mAg at room temperature-1Time capacity stability curve. As can be seen from fig. 4, the capacity retention of the material was still 90% after 250 times of charge and discharge. FIG. 5 shows Li in the present example1.19Mn0.6Ni0.2Al0.01O2Rate performance curve at room temperature when the powder is used as a positive electrode. As can be seen from FIG. 5, the highest capacity still reaches 155mAh/g when the charging rate is 5C.
Example 2: surface layer gradient doped lithium-rich layered oxide cathode material Li1.17Mn0.6Ni0.2Mg0.03O2Preparation of
(1) 0.9270g of a transition metal carbonate precursor (Mn) was weighed out0.75Ni0.25CO3) 0.0885g of Mg (NO) were added3)2·6H2O, fully and uniformly mixing, putting into a crucible, reacting for 12 hours in a box-type furnace at 350 ℃, filtering and drying after the reaction is finished, and preparing a treated precursor A;
(2) precursor A was mixed with 0.4655g of lithium salt (Li)2CO3) Mixing, adding 4g of sodium chloride and 2g of potassium chloride, fully grinding, filling into a crucible, reacting for 12 hours at 850 ℃ in a box-type furnace, cooling along with the furnace, washing with water and drying to obtain powder;
(3) grinding the powder, putting the powder into a crucible, reacting for 3 hours in a box-type furnace at 400 ℃, and cooling along with the furnace to obtain Li1.17Mn0.6Ni0.2Mg0.03O2The powder is the surface layer gradient doped lithium-rich layered oxide anode material.
The Li prepared by adopting a button cell is tested1.17Mn0.6Ni0.2Mg0.03O2Preparing the powder, conductive carbon black and a binder polyvinylidene fluoride (PVDF) into an electrode according to the mass ratio of 8:1:1, taking a metal lithium sheet as a counter electrode, and 1 mol.L-1LiPF6The volume ratio of EC, DMC and EMC (EC: DMC: EMC is 1:1:1) is electrolyte, the polypropylene material is a diaphragm, the battery test system is LAND, the charge-discharge voltage window is 2.0-4.8V, and the charge-discharge current density is 200mAg-1The material shows good electrochemical performance when being used as a positive electrode of a lithium ion batteryChemical properties. And (3) displaying a button cell test result: at 200mAg-1The first discharge specific capacity of the charge-discharge current density under the current density is 226mAhg-1(ii) a After 300 times of charge-discharge cycles, the discharge specific capacities of the materials slowly decay, and the retention rate is 95%.
Example 3: surface layer gradient doped lithium-rich layered oxide cathode material Li1.197Mn0.6Ni0.2Y0.003O2Preparation of
(1) 0.9270g of a transition metal carbonate precursor (Mn) was weighed out0.75Ni0.25CO3) 0.0118g Y (NO) was added3)3·6H2And O, fully and uniformly mixing and filling into a crucible. Reacting for 12 hours in a box-type furnace at 350 ℃, filtering and drying after the reaction is finished to prepare a treated precursor A;
(2) precursor A was mixed with 0.4655g of lithium salt (Li)2CO3) Mixing, adding 4g of sodium chloride and 2g of potassium chloride, fully grinding, filling into a crucible, reacting for 12 hours at 850 ℃ in a box-type furnace, cooling along with the furnace, washing with water and drying to obtain powder;
(3) grinding the powder, putting the powder into a crucible, reacting for 3 hours in a box-type furnace at 400 ℃, and cooling along with the furnace to obtain Li1.197Mn0.6Ni0.2Y0.003O2The powder is the surface layer gradient doped lithium-rich layered oxide anode material.
The Li prepared by adopting a button cell is tested1.197Mn0.6Ni0.2Y0.003O2Preparing the powder, conductive carbon black and a binder polyvinylidene fluoride (PVDF) into an electrode according to the mass ratio of 8:1:1, taking a metal lithium sheet as a counter electrode, and 1 mol.L-1LiPF6The volume ratio of EC, DMC and EMC (EC: DMC: EMC is 1:1:1) is electrolyte, the polypropylene material is a diaphragm, the battery test system is LAND, the charge-discharge voltage window is 2.0-4.8V, and the charge-discharge current density is 200mAg-1The material shows good electrochemical performance when being used as the anode of a lithium ion battery. And (3) displaying a button cell test result: at 200mAg-1The first discharge specific capacity of the charge-discharge current density under the current density is 215mAhg-1(ii) a After 300 times of charge-discharge cyclesAfter the ring, their discharge rate decayed slowly with a retention of 94%.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A surface layer gradient doped lithium-rich layered oxide cathode material is characterized in that: the chemical formula of the cathode material is Li1.2-xMn0.6Ni0.2MxO2M is Mg, Al, Zn, Y, Li or Ce, 0<x<0.1。
2. The preparation method of the surface gradient lithium-rich layered oxide cathode material according to claim 1, comprising the following steps:
mixing a carbonate precursor of transition metal with nitrate, and carrying out pretreatment at 100-400 ℃ in a box furnace or an oven; after the reaction is finished, washing with water to remove impurities, and drying; uniformly mixing the dried precursor A with lithium salt and molten salt, carrying out heat treatment at 700-1000 ℃, and cooling along with the furnace after the reaction is finished; washing the obtained sample with water to remove impurities, and drying to obtain powder; and (3) the powder is sintered at the temperature of 300-600 ℃, and then the surface layer gradient doped lithium-rich layered oxide anode material is prepared.
3. The method of claim 2, wherein: the carbonate precursor of the transition metal is Mn0.75Ni0.25CO3Or Mn0.75Ni0.25(OH)2(ii) a The nitrate is M (NO)3)yM is Mg, Al, Zn, Y, Li or Ce.
4. The method of claim 2, wherein: the lithium salt is more than one of lithium acetate, lithium carbonate and lithium hydroxide.
5. The method of claim 2, wherein: the molten salt is sodium chloride and potassium chloride.
6. The method of claim 2, wherein: the molar ratio of the carbonate precursor of the transition metal to the lithium salt is 1: (1-1.1); the molar ratio of the molten salt to the sum of the carbonate precursor and the lithium salt of the transition metal is 4: 1.
7. the method of claim 2, wherein: the pretreatment time is 12-24 h.
8. The method of claim 2, wherein: the heat treatment time is 8-16 h.
9. The method of claim 2, wherein: the time of the burn-back is 3-5 h.
10. The application of the surface gradient doped lithium-rich layered oxide cathode material of claim 1 in the field of lithium ion batteries.
CN201911417710.3A 2019-12-31 2019-12-31 Surface layer gradient doped lithium-rich layered oxide cathode material and preparation method and application thereof Pending CN111326730A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911417710.3A CN111326730A (en) 2019-12-31 2019-12-31 Surface layer gradient doped lithium-rich layered oxide cathode material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911417710.3A CN111326730A (en) 2019-12-31 2019-12-31 Surface layer gradient doped lithium-rich layered oxide cathode material and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN111326730A true CN111326730A (en) 2020-06-23

Family

ID=71168726

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911417710.3A Pending CN111326730A (en) 2019-12-31 2019-12-31 Surface layer gradient doped lithium-rich layered oxide cathode material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN111326730A (en)

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201311545A (en) * 2011-05-02 2013-03-16 Univ Washington Spray pyrolysis synthesis of mesoporous positive electrode materials for high energy lithium-ion batteries
CN104362332A (en) * 2014-09-25 2015-02-18 天津大学 Preparation method of lithium-rich cathode material for lithium ion battery
CN105006547A (en) * 2014-07-30 2015-10-28 香港应用科技研究院有限公司 Lithium-ion battery and coating method of electrode active material of lithium-ion battery
CN105024042A (en) * 2014-04-24 2015-11-04 法拉赛斯能源公司 Precursor of Li-ion cathode material, the preparation method thereof and Li-ion cathode material
CN105118987A (en) * 2015-09-16 2015-12-02 中国科学院化学研究所 Preparation method of high-capacity lithium-rich anode material
CN105244494A (en) * 2015-09-22 2016-01-13 华南师范大学 Improved lithium-rich manganese-based lithium-ion battery cathode material and preparation method and application
CN105580168A (en) * 2013-08-14 2016-05-11 得克萨斯州大学系统董事会 Lithium-rich layered oxide cathodes and rechargeable batteries containing lithium-rich layered oxides
CN106299328A (en) * 2015-05-14 2017-01-04 中国科学院物理研究所 Doping method, material and preparation method to lithium-rich oxide anode material
CN106876686A (en) * 2017-04-14 2017-06-20 中南大学 A kind of method for carrying out surface modification with positive electrode active materials to lithium ion battery
CN108269996A (en) * 2016-12-31 2018-07-10 北京当升材料科技股份有限公司 A kind of lithium ion battery richness manganese anode material and preparation method thereof

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201311545A (en) * 2011-05-02 2013-03-16 Univ Washington Spray pyrolysis synthesis of mesoporous positive electrode materials for high energy lithium-ion batteries
CN105580168A (en) * 2013-08-14 2016-05-11 得克萨斯州大学系统董事会 Lithium-rich layered oxide cathodes and rechargeable batteries containing lithium-rich layered oxides
CN105024042A (en) * 2014-04-24 2015-11-04 法拉赛斯能源公司 Precursor of Li-ion cathode material, the preparation method thereof and Li-ion cathode material
CN105006547A (en) * 2014-07-30 2015-10-28 香港应用科技研究院有限公司 Lithium-ion battery and coating method of electrode active material of lithium-ion battery
CN104362332A (en) * 2014-09-25 2015-02-18 天津大学 Preparation method of lithium-rich cathode material for lithium ion battery
CN106299328A (en) * 2015-05-14 2017-01-04 中国科学院物理研究所 Doping method, material and preparation method to lithium-rich oxide anode material
CN105118987A (en) * 2015-09-16 2015-12-02 中国科学院化学研究所 Preparation method of high-capacity lithium-rich anode material
CN105244494A (en) * 2015-09-22 2016-01-13 华南师范大学 Improved lithium-rich manganese-based lithium-ion battery cathode material and preparation method and application
CN108269996A (en) * 2016-12-31 2018-07-10 北京当升材料科技股份有限公司 A kind of lithium ion battery richness manganese anode material and preparation method thereof
CN106876686A (en) * 2017-04-14 2017-06-20 中南大学 A kind of method for carrying out surface modification with positive electrode active materials to lithium ion battery

Similar Documents

Publication Publication Date Title
US10741837B2 (en) Nickel-based positive electroactive materials
JP6478090B2 (en) Non-aqueous electrolyte secondary battery positive electrode active material, non-aqueous electrolyte secondary battery, and method for producing positive electrode active material for non-aqueous electrolyte secondary battery
KR101762980B1 (en) Positive electrode active material powder, method for producing same, and nonaqueous electrolyte secondary battery
CN103435105B (en) A kind of ferriferous oxide/carbon composition lithium ion battery cathode material and its preparation method and application
US7678503B2 (en) Surface and bulk modified high capacity layered oxide cathodes with low irreversible capacity loss
CN104466154B (en) A kind of preparation method of lithium ion battery anode material nickel cobalt aluminium
Yu et al. Composites Li2MnO3· LiMn1/3Ni1/3Co1/3O2: Optimized synthesis and applications as advanced high-voltage cathode for batteries working at elevated temperatures
JP5373889B2 (en) Cathode active material for lithium ion battery
CN106920964B (en) Prussian blue type sodium ion battery positive electrode material and preparation method thereof
Yang et al. Improving the cycling performance of the layered Ni-rich oxide cathode by introducing low-content Li2MnO3
JP5702289B2 (en) Method for producing nickel-cobalt-manganese multi-element positive electrode material for lithium ion battery
CN102169990B (en) Ternary cathode material and production method thereof
CN101510606B (en) Composite metal oxide coating spinelle type LiMn2O4 anode material and preparation method
CN102694167B (en) Modified lithium manganate positive pole material and preparation method thereof
CN104157831A (en) Spinel nickel manganese acid lithium and layered lithium-rich manganese-based composite cathode material with core-shell structure and preparation method thereof
CN103066269B (en) A kind of ternary positive electrode active material preparation method and battery
CN103855387A (en) Modified lithium ion battery ternary positive electrode material and preparation method thereof
CN104577093A (en) Surface coating modified lithium ion battery cathode material and preparation method thereof
KR101550741B1 (en) Manufacturing method of positive active material for lithium rechargeable batteries and positive active material made by the same
US10454108B2 (en) Bivalent metal doping for sodium manganese oxide as cathode materials for sodium ion batteries
CN104600282A (en) Surface modified lithium ion battery anode material and preparation method thereof
CN101913655B (en) Method for preparing lithium manganate cathode material by microwave sintering
CN105990577B (en) A kind of anode material for lithium-ion batteries LiNi0.6-xCo0.2Mn0.2AlxO2-yFyAnd preparation method thereof
CN104966823B (en) Material surface has nickel cobalt lithium aluminate cathode material of component concentration gradient and preparation method thereof
CN105609759A (en) High-nickel-series and full-concentration gradient lithium ion battery positive electrode material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination