CN114512661B - Modified positive electrode active material, preparation method thereof, positive electrode and lithium ion secondary battery - Google Patents

Modified positive electrode active material, preparation method thereof, positive electrode and lithium ion secondary battery Download PDF

Info

Publication number
CN114512661B
CN114512661B CN202011286688.6A CN202011286688A CN114512661B CN 114512661 B CN114512661 B CN 114512661B CN 202011286688 A CN202011286688 A CN 202011286688A CN 114512661 B CN114512661 B CN 114512661B
Authority
CN
China
Prior art keywords
positive electrode
active material
phosphate
electrode active
spinel
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.)
Active
Application number
CN202011286688.6A
Other languages
Chinese (zh)
Other versions
CN114512661A (en
Inventor
武怿达
黄学杰
詹元杰
马晓威
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.)
Institute of Physics of CAS
Songshan Lake Materials Laboratory
Original Assignee
Institute of Physics of CAS
Songshan Lake Materials Laboratory
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 Institute of Physics of CAS, Songshan Lake Materials Laboratory filed Critical Institute of Physics of CAS
Priority to CN202011286688.6A priority Critical patent/CN114512661B/en
Publication of CN114512661A publication Critical patent/CN114512661A/en
Application granted granted Critical
Publication of CN114512661B publication Critical patent/CN114512661B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • 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
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • 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
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes

Abstract

The present invention relates to a modified positive electrode active material comprising: the particle comprises primary particles of spinel phases and rock-salt-like phases, wherein the primary particles have a core-shell-like structure, the spinel phases are inner cores, and the rock-salt-like phases are distributed on the surfaces of the spinel phases to form shells; the spinel phase is formed of a lithium-containing compound having a spinel crystal structure; at least one placeholder element in Al, nb, B, si, F, S is contained in the rock-like salt phase, and occupies a 16c or 8a vacancy of the spinel octahedron or the position of oxygen ions in the spinel octahedron; the primary particles are also doped with phosphorus elements, and the phosphorus elements are distributed in a gradient manner from outside to inside. The invention further relates to a preparation method of the modified positive electrode active material, a positive electrode of a lithium ion secondary battery containing the positive electrode active material and the lithium ion secondary battery.

Description

Modified positive electrode active material, preparation method thereof, positive electrode and lithium ion secondary battery
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a modified positive electrode active material, a preparation method thereof, a positive electrode and a lithium ion secondary battery.
Background
Compared with other chargeable battery systems, the lithium ion secondary battery has the advantages of high working voltage, light weight, small volume, no memory effect, low self-discharge rate, long cycle life, high energy density and the like, and is widely applied to mobile terminals such as mobile phones, notebook computers, tablet computers and the like at presentAnd (5) a product. In recent years, electric vehicles have been rapidly developed under the promotion of various governments and automobile manufacturers in view of environmental protection, and lithium ion secondary batteries have become an ideal power source for new generation electric vehicles due to their excellent performance. Currently, positive electrode active materials of lithium ion secondary batteries of interest can be broadly divided into three categories: with lithium cobaltate (LiCoO) 2 ) As a representative layered material, lithium iron phosphate (LiFePO 4 ) Olivine-type material and lithium manganate (LiMn 2 O 4 ) Is a typical spinel structure material.
Spinel-structured high-voltage materials, which are an advanced positive electrode active material, are considered to be the positive electrode active materials most likely to be the next-generation high-performance lithium batteries. In the circulation process of the high-pressure spinel positive electrode active material, the traditional carbonate electrolyte interacts with the positive electrode active material, so that oxygen is lost from the surface of the positive electrode active material, the surface of the material is dissolved, and finally active substances are reduced. In order to solve the technical problem, it is proposed to modify the positive electrode active material by doping with elements, and the doping elements can form new chemical bonds inside and on the surface of the material so as to stabilize lattice oxygen of bulk phase and surface, but excessive doping of bulk phase elements will cause the reduction of the capacity of the positive electrode active material, affecting the electrochemical performance of the positive electrode active material.
Disclosure of Invention
Based on this, it is necessary to provide a modified positive electrode active material, a positive electrode, and a lithium ion secondary battery, which can improve the structural stability of the positive electrode active material without sacrificing the electrochemical activity of the positive electrode active material, and a method for preparing the same.
The present invention provides a modified positive electrode active material comprising:
the primary particles comprise spinel phases and rock-salt-like phases, wherein the primary particles are of spinel octahedral structures, the spinel phases are inner cores, and the rock-salt-like phases are distributed on the surfaces of the spinel phases to form shells;
the spinel phase is formed of a lithium-containing compound having a spinel crystal structure;
at least one placeholder element in Al, nb, B, si, F, S is contained in the rock-like salt phase, and occupies a 16c or 8a vacancy of the spinel octahedron or the position of oxygen ions in the spinel octahedron;
the primary particles are doped with phosphorus elements, and the phosphorus elements are distributed in a gradient manner from outside to inside.
In one embodiment, the lithium-containing compound is a lithium nickel manganese oxide compound having the formula Li 1+x Ni 0.5-y Mn 1.5-z O u Wherein, -0.2.ltoreq.x.ltoreq.0.2, -0.2.ltoreq.y.ltoreq.0.2, -0.2.ltoreq.z.ltoreq. 0.2,3.8.ltoreq.u.ltoreq.4.2.
In one embodiment, the spinel phase has a thickness of 0.1 μm to 30 μm.
In one embodiment, the rock-like salt phase has a thickness of 0.5nm to 50nm.
In one embodiment, the gradient distribution structure of the phosphorus element in the primary particles is a phosphorus gradient doped layer, and the thickness of the phosphorus gradient doped layer is 0.5 nm-40 nm.
In one embodiment, the primary particles further comprise one or more elements of magnesium, calcium, iron, copper, zinc, titanium, zirconium, cobalt, cadmium, and vanadium.
In one embodiment, the doping amount of the phosphorus element in the primary particles is gradually decreased from outside to inside.
The invention also provides a preparation method of the modified positive electrode active material, which comprises the following steps:
providing a lithium-containing compound;
mixing a phosphorus source, a rock-like salt phase inducer and the lithium-containing compound to obtain a mixture; and
sintering the mixture at 600-1200 deg.c for 0.5-10 hr.
In one embodiment, the phosphorus source comprises one or more of nickel phosphate, cobalt phosphate, manganese phosphate, magnesium phosphate, calcium phosphate, iron phosphate, copper phosphate, zinc phosphate, titanium phosphate, zirconium phosphate, lithium phosphate, cobalt pyrophosphate, nickel pyrophosphate, manganese pyrophosphate, magnesium pyrophosphate, calcium pyrophosphate, iron pyrophosphate, copper pyrophosphate, zinc pyrophosphate, titanium pyrophosphate, zirconium pyrophosphate, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, lithium dihydrogen phosphate, dilithium hydrogen phosphate, lithium pyrophosphate, pyrophosphoric acid, phosphoric acid, and phosphorus pentoxide.
In one embodiment, the rock-like salt phase inducer is one or more of an oxide, a simple substance, a salt, and a compound of the placeholder element.
In one embodiment, the lithoid phase inducing agent further comprises one or more of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, formic acid, oxalic acid, and citric acid.
In one embodiment, the mass ratio of the phosphorus source, the rock-like salt phase inducer and the lithium-containing compound is (1-30): (1-30): 2000.
the invention also provides a positive electrode of the lithium ion secondary battery, which comprises a positive electrode current collector and a positive electrode active material layer positioned on the positive electrode current collector, wherein the positive electrode active material layer comprises the modified positive electrode active material.
The present invention also provides a lithium ion secondary battery comprising:
a positive electrode as described above;
a negative electrode including a negative electrode current collector and a negative electrode active material layer on the negative electrode current collector;
separator and electrolyte.
The primary particles of the modified positive electrode active material provided by the invention have a shell-core-like structure of a spinel-phase inner core and a rock-salt-like phase outer shell, wherein the rock-salt-like phase outer shell contains a placeholder element, and the primary particles also contain gradient-distributed phosphorus elements. According to the structure, a rock-like salt phase shell containing a placeholder element is constructed on the surface of an original electrode material, and the placeholder element induces a crystal structure on the surface of the original electrode material to generate phase change due to the introduction of the placeholder element, so that the lattice constant of the surface of the original electrode material is changed, and the barrier that phosphorus element is doped into the electrode material structure is reduced, so that the phosphorus element can be doped into the positive electrode active material in a gradient distribution mode. The gradient-distributed phosphorus element relieves the structural stress generated in the deintercalation process of lithium ions, and reduces the reactivity between the positive electrode active material and the electrolyte. Meanwhile, the occupied element can further improve the electronic conductivity and interface stability of the positive electrode active material. The gradient doped phosphorus element and the placeholder element in the rock-like salt phase can synergistically improve the stability of the surface structure of the positive electrode active material, so that the capacity retention rate and the charge-discharge coulomb efficiency of the battery are improved. Meanwhile, each element in the plurality of occupied elements has unique effects, the lattice constant of the aluminum element can be stabilized, the ginger Taylor effect of a spinel structure is reduced, the long circulation of the lithium nickel manganese oxide is greatly beneficial, the circulation of the niobium element can be improved, the morphology of the synthesized lithium nickel manganese oxide can be changed by the niobium element, and the morphology, the particle size and the tap of the finally synthesized lithium nickel manganese oxide can be effectively controlled. For nonmetallic B, si, F, S elements, the electrolyte can generate an interface film containing B, si, F, S under high voltage, and the interface film containing the elements has higher rate capability and better stability.
Drawings
FIG. 1 is a STEM chart of the modified positive electrode active material prepared in example 1;
FIG. 2 is a STEM line scan of the modified positive electrode active material prepared in example 1;
FIG. 3 is a STEM chart of the surface of the modified positive electrode active material prepared in example 2;
FIG. 4 is a graph showing the relative content change of phosphorus element on the surface of the modified positive electrode active material prepared in example 2, which is characterized by XPS at different etching depths;
FIG. 5 is a STEM chart of the surface of the modified positive electrode active material prepared in example 3;
fig. 6 is an XPS diagram of the F element on the surface of the modified cathode active material prepared in example 4.
Detailed Description
In order that the invention may be readily understood, a more complete description of the invention will be rendered by reference to the appended drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Except where shown or otherwise indicated in the operating examples, all numbers expressing quantities of ingredients, physical and chemical properties, and so forth, used in the specification and claims are to be understood as being modified in all instances by the term "about". For example, therefore, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be varied appropriately by those skilled in the art utilizing the teachings disclosed herein seeking to obtain the desired properties. The use of numerical ranges by endpoints includes all numbers subsumed within that range and any range within that range, e.g., 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, 5, and the like.
A core-shell structure is generally defined as an orderly assembled structure formed by one material encapsulating another material by chemical bonds or other forces. The core-shell like structure "core" and "shell" as defined in the present invention are virtually integral. The modified positive electrode active material structure of the present invention includes two phases, resulting in a microstructure of the surface layer different from that of the interior of the material, the interior of the material thus formed is referred to as "core", the surface layer is referred to as "shell", and the material of such structure is defined as a core-shell-like structure.
The "lithoid phase" is formed by occupying the 16c or 8a position of the spinel octahedron with an element.
The embodiment of the invention provides a modified positive electrode active material, which comprises the following components:
the particle comprises primary particles of spinel phases and rock-salt-like phases, wherein the primary particles have a core-shell-like structure, the spinel phases are inner cores, and the rock-salt-like phases are distributed on the surfaces of the spinel phases to form shells;
the spinel phase is formed of a lithium-containing compound having a spinel crystal structure including lithium, nickel and manganese,
at least one placeholder element in Al, nb, B, si, F, S is contained in the rock-like salt phase, and occupies a 16c or 8a vacancy of the spinel octahedron or the position of oxygen ions in the spinel octahedron;
the primary particles are doped with phosphorus elements, and the phosphorus elements are distributed in a gradient manner from outside to inside.
The primary particles of the modified positive electrode active material provided by the embodiment of the invention have a shell-core-like structure of a spinel-phase inner core and a rock-salt-like phase outer shell, wherein the rock-salt-like phase outer shell contains a placeholder element, and the primary particles also contain gradient-distributed phosphorus elements. According to the structure, a rock-like salt phase shell containing a placeholder element is constructed on the surface of an original electrode material, and the placeholder element induces a crystal structure on the surface of the original electrode material to generate phase change due to the introduction of the placeholder element, so that the lattice constant of the surface of the original electrode material is changed, and the barrier that phosphorus element is doped into the electrode material structure is reduced, so that the phosphorus element can be doped into the positive electrode active material in a gradient distribution mode. The gradient-distributed phosphorus element relieves the structural stress generated in the deintercalation process of lithium ions, and reduces the reactivity between the positive electrode active material and the electrolyte. Meanwhile, the occupied element can further improve the electronic conductivity and interface stability of the positive electrode active material. The gradient doped phosphorus element and the placeholder element in the rock-like salt phase can synergistically improve the stability of the surface structure of the positive electrode active material, so that the capacity retention rate and the charge-discharge coulomb efficiency of the battery are improved.
The primary particles refer to the smallest units constituting the positive electrode active material, and in particular, refer to the smallest units determinable based on the geometric configuration of the appearance. The aggregate of primary particles is a secondary particle. The primary particles have a core-shell-like structure in which a spinel phase inner core and a rock-salt-like phase outer shell are integrated, there is no grain boundary at a boundary between the spinel phase and the rock-salt-like phase, and the spinel phase and the rock-salt-like phase cannot be separated from each other by oxygen bonding. The positive electrode active material having the above-described configuration has higher structural stability.
Preferably, the lithium-containing compound is a lithium nickel manganese oxide compound. More preferably, the lithium-containing compound may have the formula Li 1+x Ni 0.5-y Mn 1.5-z O u Wherein, -0.2.ltoreq.x.ltoreq.0.2, -0.2.ltoreq.y.ltoreq.0.2, -0.2.ltoreq.z.ltoreq. 0.2,3.8.ltoreq.u.ltoreq.4.2. The values of x, y and z may vary depending on the ratio between the elements, but are set within a range such that the compound represented by the chemical formula may take on a spinel structure.
The occupying element is preferably Al, which is more beneficial to improving the structural stability of the positive electrode active material and reducing the barrier of doping phosphorus into a spinel structure.
The thickness of the spinel phase may be any value between 0.1 μm and 30 μm, and may also include, for example, 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 26 μm, 27 μm, 28 μm, 29 μm.
The rock-like salt phase may have a thickness of any value between 0.5nm and 50nm, and may further include, for example, 0.5nm, 1nm, 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm, 19nm, 20nm, 21nm, 22nm, 23nm, 24nm, 25nm, 26nm, 27nm, 28nm, 29nm, 30nm, 31nm, 32nm, 33nm, 34nm, 35nm, 36nm, 37nm, 38nm, 39nm, 40nm, 41nm, 42nm, 43nm, 44nm, 45nm, 46nm, 47nm, 48nm, 49nm, 50nm.
The modified positive electrode active material provided by the invention is doped with phosphorus element, but is different from the phosphate coated positive electrode active material in the prior art. The phosphate coated positive electrode active material is a material formed by coating a spinel positive electrode material with phosphate crystal structure or amorphous phosphate, and the surface of the material is visible by a transmission electron microscope. The modified positive electrode active material provided by the invention has the advantages that the phosphorus element is doped in the primary particles, and the phosphorus element is doped into the spinel structure from the surface of the primary particles to the inside in a gradient manner.
The spinel phase and the rock-salt-like phase of the primary particles are both doped with phosphorus elements, but the phosphorus elements are preferentially doped in the rock-salt-like phase. The doping amount of the phosphorus element in the primary particles is gradually decreased from outside to inside.
The structure in which the phosphorus element in the primary particles is distributed in a gradient manner can be defined as a phosphorus gradient doped layer, and the thickness of the phosphorus gradient doped layer can be any value between 0.5nm and 40nm, and for example, 0.5nm, 1nm, 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm, 19nm, 20nm, 21nm, 22nm, 23nm, 24nm, 25nm, 26nm, 27nm, 28nm, 29nm, 30nm, 32nm, 35nm and 38nm can be further included.
The primary particles also contain one or more elements of magnesium, calcium, iron, copper, zinc, titanium, zirconium, cobalt, cadmium and vanadium.
The positive electrode material, the rock-like salt phase surface layer and the phosphorus gradient doped layer can be characterized by a characterization method commonly used in the field, for example, the positive electrode material can be characterized by a Scanning Transmission Electron Microscope (STEM) and an X-ray photoelectron spectroscopy microscope (XPS), wherein the STEM can be used for accurately seeing the rock-like salt phase distribution of the surface due to the fact that part of occupied elements occupy the 16c or 8a positions of the spinel octahedron, and the STEM line scanning can also prove the gradient distribution of the phosphorus elements. Meanwhile, the gradient distribution of the phosphorus element in the phosphorus gradient doped layer can be proved by utilizing the etching analysis of the X-ray photoelectron spectroscopy. Specific characterization methods can be found in M.Lin, L.Ben, Y.Sun, H.Wang, Z.Yang, L.Gu, X.Yu, X. -Q.Yang, H.Zhao, R.Yu, M.Armand, X.Huang, insight into the Atomic Structure of High-VoltagespinelLiNi 0.5 Mn 1.5 O 4 Cathode Material in the First Cycle.Chemistry ofMaterials 27,292-303(2015)，Y.Wu,L.Ben,H.Yu,W.Qi,Y.Zhan,W.Zhao,X.Huang,Understanding the Effect of Atomic-Scale Surface Migration ofBridging Ions inBinding Li3PO4 to the Surface of Spinel Cathode Materials.Acs Applied Materials&Interfaces 11,6937-6947(2019)。
The invention also provides a preparation method of the modified positive electrode active material, which comprises the following steps:
s10, providing a lithium-containing compound;
s20, mixing a phosphorus source, a rock-like salt phase inducer and the lithium-containing compound to obtain a mixture; and
s30, sintering the mixture at 600-1200 ℃ for 0.5-10 hours.
The lithium-containing compound may be prepared by methods known to those skilled in the art. For example, the preparation can be carried out by a low-temperature solid phase method. Specifically, a precursor can be prepared by mixing nickel salt, manganese salt, lithium hydroxide and oxalic acid and ball milling, and then the precursor is calcined at high temperature to obtain the lithium-containing compound.
The phosphorus source may include one or more of nickel phosphate, cobalt phosphate, manganese phosphate, magnesium phosphate, calcium phosphate, iron phosphate, copper phosphate, zinc phosphate, titanium phosphate, zirconium phosphate, lithium phosphate, cobalt pyrophosphate, nickel pyrophosphate, manganese pyrophosphate, magnesium pyrophosphate, calcium pyrophosphate, iron pyrophosphate, copper pyrophosphate, zinc pyrophosphate, titanium pyrophosphate, zirconium pyrophosphate, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, lithium dihydrogen phosphate, dilithium hydrogen phosphate, lithium pyrophosphate, pyrophosphoric acid, phosphoric acid, and phosphorus pentoxide. Preferably, the phosphorus source is one or more of titanium phosphate, copper phosphate, cobalt phosphate and phosphoric acid.
The rock-like salt phase inducer can be one or more of an oxide, a simple substance and a salt of the placeholder element. For example, al 2 O 3 、Nb 2 O、Nb 2 O 5 、B 2 O 3 、SiO 2 、Al(OH) 3 、H3BO3、NaAlO 2 、Na 2 SiO 3 、NH 4 F. S, etc.
The rock-salt-like phase inducer may also include one or more of an organic acid or an inorganic acid, such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, formic acid, oxalic acid, citric acid, and the like. The organic or inorganic acid may further promote the generation of rock-like salt phases.
The mass ratio of the phosphorus source, the rock-like salt phase inducer and the lithium-containing compound can be (1-30): (1-30): 2000, for example, may also be 1:1:50,1:1:80,1:1:100,1:1:150,1:1:200,1:1:250,1:1:300,1:1:350,1:1:400,1:1:500,1:1:600,1:1:700,1:1:800,1:1:900,1:1:1000,1:1:1200,1:1:1500,1:1:1800.
In step S20, the phosphorus source, the rock-like salt phase inducer, and the lithium-containing compound may be mixed by methods known to those skilled in the art, such as mechanical mixing, ultrasonic, ball milling, and the like.
The sintering in step S30 may be performed under oxygen, air, or an inert atmosphere (e.g., nitrogen or argon) and an atmosphere containing oxygen. Preferably, the specific operation of the sintering process is as follows: heating to 600-1200 deg.c at the heating rate of 0.5-10 deg.c/min, sintering for 0.5-10 hr, and cooling to room temperature at the cooling rate of 0.5-10 deg.c/min.
The invention also provides a positive electrode of the lithium ion secondary battery, which comprises a positive electrode current collector and a positive electrode active material layer positioned on the positive electrode current collector, wherein the positive electrode active material layer comprises the modified positive electrode active material.
As the positive electrode current collector, a conductive element formed of a highly conductive metal as used in the positive electrode of the lithium ion secondary battery of the related art is preferable. For example, aluminum or an alloy including aluminum as a main component may be used. The shape of the positive electrode current collector is not particularly limited, as it may vary depending on the shape of the lithium ion secondary battery, etc. For example, the positive electrode current collector may have various shapes such as a rod shape, a plate shape, a sheet shape, and a foil shape.
The positive electrode active material layer further includes a conductive additive and a binder.
The conductive additive may be a conductive additive conventional in the art, and the present invention is not particularly limited thereto. For example, in some embodiments, the conductive additive is carbon black (e.g., acetylene black or Ketjen black).
The binder may be a binder conventional in the art, and the present invention is not particularly limited, and may be composed of polyvinylidene fluoride (PVDF), and may also be composed of carboxymethyl cellulose (CMC) and Styrene Butadiene Rubber (SBR). In some embodiments, the binder is polyvinylidene fluoride (PVDF).
The present invention also provides a lithium ion secondary battery comprising:
a positive electrode as described above;
a negative electrode including a negative electrode current collector and a negative electrode active material layer on the negative electrode current collector;
separator and electrolyte.
As a current collector of the negative electrode,
the negative electrode, separator and electrolyte may employ a negative electrode current collector, separator and electrolyte material conventional in the art, and the present invention is not particularly limited thereto.
The negative electrode current collector may be copper, and the shape of the negative electrode current collector is also not particularly limited, and may be in the shape of a rod, a plate, a sheet, and a foil, which may vary depending on the shape of the lithium ion secondary battery, etc. The anode active material layer includes an anode active material, a conductive additive, and a binder. The anode active material, the conductive additive, and the binder are also conventional materials in the art. In some embodiments, the negative electrode active material is lithium metal. The conductive additive and the binder are described above and are not described in detail herein.
The separator may be a separator used in a usual lithium ion secondary battery, and examples thereof include microporous films made of polyethylene or polypropylene; porous polyethylene films and polypropylene multilayer films; a nonwoven fabric formed of polyester fibers, aramid fibers, glass fibers, and the like; and a base film formed by attaching ceramic fine particles such as silica, alumina, titania, etc. to the surface of the base film. In some embodiments, the separator is a three-layer film of PP/PE/PP coated on both sides with aluminum oxide.
The electrolyte can beTo include an electrolyte and a non-aqueous organic solvent. The electrolyte is preferably LiPF 6 、LiBF 4 、LiSbF 6 、LiAsF 6 . The nonaqueous organic solvent may be a carbonate, an ester, or an ether. Among them, carbonates such as Ethylene Carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC) and Ethyl Methyl Carbonate (EMC) may be preferably used.
The following examples are intended to illustrate the present invention in further detail to aid those skilled in the art and researchers in further understanding the present invention, and the technical conditions and the like are not to be construed as limiting the present invention in any way. Any modification made within the scope of the claims of the present invention is within the scope of the claims of the present invention.
In the following examples, STEM was performed using a spherical aberration correcting scanning transmission microscope model JEM ARM200F (JEOL, tokyo, japan); x-ray photoelectron Spectrometry (XPS) an ESCALAB 250 model X-ray photoelectron spectrometer manufactured by Thermo Fisher company was used to study the type and chemical environment of the surface elements of the powder sample, wherein the X-ray radiation source was MgK alpha.
Example 1
9g of LiNi 0.5 Mn 1.5 O 4 Material, 0.05g B 2 O 3 And 0.1g (NH) 4 ) 2 HPO 4 And uniformly mixing, calcining the obtained mixture in oxygen at 600 ℃ for 5 hours, wherein the heating rate is 3 ℃/min, and the cooling rate is 5 ℃/min, so as to obtain the modified positive electrode active material.
Fig. 1 shows STEM diagrams of the modified cathode active material prepared in example 1. From the STEM diagram of the modified cathode active material of fig. 1, it can be seen that the material surface has a rock-like salt phase generated by occupying the 16c atoms of spinel octahedron, and the thickness of the rock-like salt phase is about 10nm.
Fig. 2 is a STEM line scan of the phosphorus content of the surface of the modified cathode active material prepared in example 1, and it can be seen from fig. 2 that the doped lithium nickel manganese oxide has no coating layer on the surface, and in combination with fig. 1, the phosphorus is distributed in a rock-like salt phase, and the phosphorus content gradually decreases from the surface to the inside.
Example 2
9g of LiNi 0.4 Mn 1.6 O 4 Material, 0.2. 0.2g H 3 PO 4 And 0.267g Nb 2 O 5 And uniformly mixing, calcining the obtained mixture in oxygen at 800 ℃ for 5 hours, wherein the heating rate is 3 ℃/min, and the cooling rate is 5 ℃/min, so as to obtain the modified positive electrode active material.
Fig. 3 shows STEM diagrams of the modified cathode active material prepared in example 2. From the figure, it can be seen that the material surface has a rock-like salt phase with spinel octahedral 8a atoms occupying the sites, and the thickness of the rock-like salt phase is about 5nm.
Fig. 4 shows the relative content change of the surface phosphorus element obtained by the XPS characterization of the modified cathode active material prepared in example 2 at different etching depths, and we can see that the content of the phosphorus element continuously decreases from the surface to the inside along with the increase of the etching depth.
Example 3
9g of LiNi 0.4 Mn 1.6 O 4 Material, 0.1g SiO 2 And 0.133g (NH) 4 ) 2 HPO 4 And 20ml of deionized water were added to the beaker and mixed uniformly, and the beaker was placed in an oil bath at 120 ℃ and heated with stirring for 5 hours to obtain a dry mixture. Calcining the obtained mixture in oxygen for 5 hours at 850 ℃, wherein the heating rate is 3 ℃/min, and the cooling rate is 5 ℃/min, so as to obtain the modified positive electrode active material.
Fig. 5 shows STEM diagrams of the modified cathode active material prepared in example 3. From the figure, it can be seen that the surface of the material has rock-like salt phases with 2-3 nm spinel octahedra 8a and 16c atoms occupying positions, and the thickness of the rock-like salt phase on the surface is about 2nm.
Example 4
9g of LiNi 0.4 Mn 1.6 O 4 Material, 0.2. 0.2g H 3 PO 4 And 0.267g NH 4 F, uniformly mixing, calcining the obtained mixture in oxygen at 800 ℃ for 5 hours, wherein the heating rate is 3 ℃/min, and the cooling rate is 5 ℃/min, so as to obtain the modified positive electrode active material.
Fig. 6 shows XPS spectra of the modified cathode active material prepared in example 4, and the result shows that the surface of the material contains F element.
Example 5
9g of LiNi 0.5 Mn 1.5 O 4 Material, 0.03g Al 2 O 3 And 0.125g (NH) 4 ) 2 HPO 4 And uniformly mixing, calcining the obtained mixture in air at 800 ℃ for 5 hours, wherein the heating rate is 3 ℃/min, and the cooling rate is 5 ℃/min, so as to obtain the modified positive electrode active material.
Example 6
9g of LiNi 0.5 Mn 1.5 O 4 Material, 0.015g g S and 0.15g (NH 4 ) 2 HPO 4 And uniformly mixing, namely calcining the obtained mixture in a closed space at 825 ℃ for 5 hours, wherein the heating rate is 3 ℃/min, and the cooling rate is 5 ℃/min, so as to obtain the modified positive electrode active material.
Comparative example 1
The preparation process was substantially the same as in example 1, except that no phosphorus source (NH 4 ) 2 HPO 4 。
Comparative example 2
The preparation process is basically the same as that of example 1, except that the rock-like salt phase inducer B 2 O 3 And replaced with hydrochloric acid.
Performance testing
The positive electrode active materials prepared in examples 1 to 4 and comparative examples 1 to 2 were assembled into button cells according to the following procedure.
(1) Preparation of positive electrode sheet
The positive electrode active material prepared in the example, carbon black as a conductive additive and polyvinylidene fluoride (PVDF) as a binder were dispersed in N-methylpyrrolidone (NMP) in a weight ratio of 80:10:10, and uniformly mixed to prepare a uniform positive electrode slurry. Uniformly coating the uniform positive electrode slurry on an aluminum foil current collector with a thickness of 15 μm, drying at 55deg.C to form a sheet with a thickness of 100 μm, and rolling the sheet under a roll press (pressure of about 1MPa×1.5 cm) 2 ) Cutting into diameter ofIs a wafer of (a)Then placing the anode plate in a vacuum oven to bake for 6 hours at 120 ℃, naturally cooling, and taking out the anode plate to be used as an anode plate in a glove box.
(2) Assembled lithium ion secondary battery
In a glove box filled with inert atmosphere, taking metallic lithium as a negative electrode of a battery, taking a three-layer film of PP/PE/PP with aluminum oxide coated on two sides as a diaphragm, placing the three-layer film between the positive electrode and the negative electrode, dripping a commonly used carbonate electrolyte, taking the positive electrode plate prepared in the step (1) as the positive electrode, and assembling the button battery with the model CR 2032.
High temperature cycle test:
and standing the prepared button cell for 10 hours at room temperature (25 ℃), then performing charge-discharge activation on the button cell, and then performing charge-discharge cycle test on the prepared button cell by adopting a blue cell charge-discharge tester. First, the cycle was continued at 0.1C for 1 week and then at 0.2C for 4 weeks at room temperature (25 ℃) with the charge-discharge voltage of the battery controlled to be in the range of 3.5V to 4.9V. Then, the button cell was transferred to a high temperature environment of 55 ℃ and the cycle was continued for 50 weeks at a rate of 0.2C while controlling the charge-discharge voltage range of the battery to be still 3.5V to 4.9V.
By LiNi 0.5 Mn 1.5 O 4 、LiNi 0.4 Mn 1.6 O 4 As a control, the measured data are listed in table 1.
TABLE 1 electrochemical Properties of Positive electrode active materials of various examples of the invention
The results show the original LiNi 0.5 Mn 1.5 O 4 Material, original LiNi 0.4 Mn 1.6 O 4 Materials and cathode active materials prepared in comparative examples 1 and 2 were assembledThe capacity of the battery decays rapidly after 50 weeks under the high-temperature test environment of 55 ℃, because the capacity of the material decays rapidly due to electrolyte decomposition and dissolution of the cathode active material Mn/Ni; the materials prepared in examples 1 to 4 after gradient doping with P have almost no attenuation of capacity after 50 weeks in a high temperature test environment at 55 ℃, because the adverse side reaction between the positive electrode active material and the electrolyte is relieved after gradient doping with phosphorus, and the decomposition of the electrolyte and the dissolution of Mn/Ni are inhibited, thereby improving the cycle stability of the battery.
The table shows that after phosphorus doping and surface modification of the placeholder element (Al, nb, B, si, F, S), the adverse side reaction between the positive electrode active material and the electrolyte is relieved, and the decomposition of the electrolyte and the dissolution of Mn/Ni of the positive electrode active material are inhibited, so that the cycle stability of the battery is improved. Meanwhile, the gradient phosphorus doping and the placeholder element (Al, nb, B, si, F, S) have a synergistic effect, and compared with the single phosphorus doping and the placeholder element (Al, nb, B, si, F, S) surface modification, the cyclic stability of the material jointly modified by the gradient phosphorus doping and the placeholder element is obviously improved.
By LiNi 0.5 Mn 1.5 O 4 As a control, the electrochemical data are shown in table 2.
TABLE 2 electrochemical rate performance of the cathode active materials of the various embodiments of the invention
The table above shows that the rate capability of the lithium nickel manganese oxide material is increased on the surface of the material through nonmetallic elements such as boron.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (12)

1. A modified positive electrode active material, characterized in that the modified positive electrode active material comprises:
the particle comprises primary particles of spinel phases and rock-like salt phases, wherein the spinel phases are inner cores, and the rock-like salt phases are distributed on the surfaces of the spinel phases to form shells;
the spinel phase is formed of a lithium-containing compound having a spinel crystal structure;
the rock-like salt phase comprises at least one placeholder element in Al, nb, B, si, F, S, and is induced and generated by at least one of an oxidant of the placeholder element, a simple substance of the placeholder element and a salt, and occupies a 16c or 8a vacancy of the spinel octahedron or a position of an oxygen ion in the spinel octahedron; the primary particles are doped with phosphorus elements, and the phosphorus elements are distributed in a gradient manner from outside to inside.
2. The modified positive electrode active material according to claim 1, wherein the lithium-containing compound is a lithium nickel manganese oxide compound having a chemical formula of Li 1+x Ni 0.5-y Mn 1.5-z O u Wherein, -0.2.ltoreq.x.ltoreq.0.2, -0.2.ltoreq.y.ltoreq.0.2, -0.2.ltoreq.z.ltoreq. 0.2,3.8.ltoreq.u.ltoreq.4.2.
3. The modified cathode active material according to claim 1, wherein the spinel phase has a thickness of 0.1 μm to 30 μm.
4. The modified cathode active material of claim 1, wherein the rock-like salt phase has a thickness of 0.5nm to 50nm.
5. The modified cathode active material according to claim 1, wherein the structure in which the phosphorus element in the primary particles is distributed in a gradient is a phosphorus gradient doped layer, and the thickness of the phosphorus gradient doped layer is 0.5nm to 40nm.
6. The modified cathode active material according to claim 1, wherein the primary particles further contain one or more elements of magnesium, calcium, iron, copper, zinc, titanium, zirconium, cobalt, cadmium, and vanadium.
7. A method for producing the modified positive electrode active material according to any one of claims 1 to 6, comprising the steps of:
providing a lithium-containing compound;
mixing a phosphorus source, a rock-like salt phase inducer and the lithium-containing compound to obtain a mixture; and
heating the mixture to 600-1200 ℃ at a heating rate of 0.5-10 ℃/min, sintering for 0.5-10 hours, and then cooling to room temperature at a cooling rate of 0.5-10 ℃/min;
the rock-like salt phase inducer is at least one of oxides, simple substances and salts of the placeholder elements.
8. The method for producing a modified positive electrode active material according to claim 7, wherein the phosphorus source comprises one or more of nickel phosphate, cobalt phosphate, manganese phosphate, magnesium phosphate, calcium phosphate, iron phosphate, copper phosphate, zinc phosphate, titanium phosphate, zirconium phosphate, lithium phosphate, cobalt pyrophosphate, nickel pyrophosphate, manganese pyrophosphate, magnesium pyrophosphate, calcium pyrophosphate, iron pyrophosphate, copper pyrophosphate, zinc pyrophosphate, titanium pyrophosphate, zirconium pyrophosphate, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, lithium dihydrogen phosphate, dilithium hydrogen phosphate, lithium pyrophosphate, pyrophosphoric acid, phosphoric acid, and phosphorus pentoxide.
9. The method of preparing a modified cathode active material according to claim 7, wherein the rock-like salt phase inducer further comprises one or more of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, formic acid, oxalic acid, and citric acid.
10. The method for producing a modified positive electrode active material according to any one of claims 7 to 9, wherein the mass ratio of the phosphorus source, the rock-like salt phase inducer and the lithium-containing compound is (1 to 30): (1-30): 2000.
11. a positive electrode of a lithium ion secondary battery, characterized by comprising a positive electrode current collector and a positive electrode active material layer on the positive electrode current collector, the positive electrode active material layer comprising the modified positive electrode active material according to claims 1 to 6.
12. A lithium ion secondary battery, characterized by comprising:
the positive electrode of claim 11;
a negative electrode including a negative electrode current collector and a negative electrode active material layer on the negative electrode current collector;
separator and electrolyte.
CN202011286688.6A 2020-11-17 2020-11-17 Modified positive electrode active material, preparation method thereof, positive electrode and lithium ion secondary battery Active CN114512661B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011286688.6A CN114512661B (en) 2020-11-17 2020-11-17 Modified positive electrode active material, preparation method thereof, positive electrode and lithium ion secondary battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011286688.6A CN114512661B (en) 2020-11-17 2020-11-17 Modified positive electrode active material, preparation method thereof, positive electrode and lithium ion secondary battery

Publications (2)

Publication Number Publication Date
CN114512661A CN114512661A (en) 2022-05-17
CN114512661B true CN114512661B (en) 2023-10-20

Family

ID=81546735

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011286688.6A Active CN114512661B (en) 2020-11-17 2020-11-17 Modified positive electrode active material, preparation method thereof, positive electrode and lithium ion secondary battery

Country Status (1)

Country Link
CN (1) CN114512661B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115020673A (en) * 2022-07-01 2022-09-06 合肥国轩高科动力能源有限公司 Modified nickel-cobalt-manganese ternary cathode material, preparation method thereof and lithium ion battery
CN116885156B (en) * 2023-09-07 2024-02-20 宁德时代新能源科技股份有限公司 Lithium nickel manganese oxide material, preparation method, secondary battery and power utilization device
CN117080535B (en) * 2023-10-19 2023-12-22 中创新航科技集团股份有限公司 Cylindrical battery

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015099662A (en) * 2013-11-18 2015-05-28 旭化成株式会社 Positive electrode active material, positive electrode, and nonaqueous electrolyte secondary battery
CN110911687A (en) * 2019-12-09 2020-03-24 中南大学 Rare earth element modified lithium ion battery positive electrode material, and preparation method and application thereof
CN111799468A (en) * 2020-08-13 2020-10-20 中南大学 Lithium ion battery anode material jointly modified by ionic conductor and heterostructure, preparation method and application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015099662A (en) * 2013-11-18 2015-05-28 旭化成株式会社 Positive electrode active material, positive electrode, and nonaqueous electrolyte secondary battery
CN110911687A (en) * 2019-12-09 2020-03-24 中南大学 Rare earth element modified lithium ion battery positive electrode material, and preparation method and application thereof
CN111799468A (en) * 2020-08-13 2020-10-20 中南大学 Lithium ion battery anode material jointly modified by ionic conductor and heterostructure, preparation method and application

Also Published As

Publication number Publication date
CN114512661A (en) 2022-05-17

Similar Documents

Publication Publication Date Title
KR102256298B1 (en) Nickel-based active material precursor for lithium secondary battery, preparing method thereof, nickel-based active material for lithium secondary battery formed thereof, and lithium secondary battery comprising positive electrode including the nickel-based active material
CN114512661B (en) Modified positive electrode active material, preparation method thereof, positive electrode and lithium ion secondary battery
US7473493B2 (en) Process of preparing active material for battery and active material for battery prepared therefrom
EP2639865B1 (en) Positive active material, method of preparing the same, and lithium secondary battery using the same
CN112151773B (en) Positive active material, preparation method thereof and lithium battery
EP2741353A1 (en) Cathode active material, method for preparing the same, and lithium secondary batteries including the same
JP2018092931A (en) Nickel-based active material for lithium secondary battery, manufacturing method thereof, and lithium secondary battery including positive electrode including the same
CN114512659B (en) Modified spinel structure positive electrode active material, preparation method thereof, positive electrode and lithium ion secondary battery
CN114512642B (en) Positive electrode active material, preparation method thereof, positive electrode and lithium ion secondary battery
CN111193018B (en) Lithium battery positive active material and preparation method and application thereof
KR102580242B1 (en) Cobalt oxide for lithium secondary battery, lithium cobalt oxide for lithium secondary battery formed from the same, preparing method of the lithium cobalt oxide, and lithium secondary battery including positive electrode comprising the lithium cobalt oxide
KR102178807B1 (en) Positive electrode active material for rechargable lithium battery, method for manufacturing the same, and rechargable lithium battery including the same
KR20150090963A (en) Positive electrode active material for rechargable lithium battery, method for synthesis the same, and rechargable lithium battery including the same
KR20140025160A (en) Composite negative electrode active material, method for preparing the same, and lithium battery including the same
CN111933930B (en) Positive electrode active material, preparation method thereof, secondary battery positive electrode and lithium battery
CN114506877B (en) Preparation method of positive electrode active material, positive electrode and lithium ion secondary battery
CN114512660B (en) Positive active material precursor, preparation method thereof and positive active material
JP2004175609A (en) Lithium cobaltate used for positive electrode of lithium ion battery, its manufacturing process and lithium ion battery
KR20180074340A (en) Method of manufacturing positive active material for lithium secondary battery
CN114512644B (en) Positive electrode active material, preparation method thereof, positive electrode and lithium ion secondary battery
CN114512643B (en) Positive electrode active material, preparation method thereof, positive electrode and lithium ion secondary battery
CN116477661A (en) Lithium supplementing material and preparation method and application thereof
Chen et al. Enhanced electrochemical performance of Li 1.2 Ni 0.2 Mn 0.6 O 2 cathode materials through facile layered/spinel phase tuning
KR20160069325A (en) Negative active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same
KR20160121833A (en) Phosphate positive electrode active material for lithium secondary battery and a method of manufacturing the same

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
TA01 Transfer of patent application right

Effective date of registration: 20221111

Address after: Building A1, innovation city, Songshanhu University, Dongguan, Guangdong 523000

Applicant after: Material Laboratory of Songshan Lake

Applicant after: INSTITUTE OF PHYSICS, CHINESE ACADEMY OF SCIENCES

Address before: Building A1, innovation city, Songshanhu University, Dongguan, Guangdong 523000

Applicant before: Material Laboratory of Songshan Lake

TA01 Transfer of patent application right
GR01 Patent grant
GR01 Patent grant