CN114512661A - 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 PDFInfo
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Abstract
The present invention relates to a modified positive electrode active material comprising: the primary particles comprise a spinel phase and a rock-salt-like phase, the primary particles have a core-shell-like structure, the spinel phase is a core, and the rock-salt-like phase is distributed on the surface of the spinel phase to form an outer shell; the spinel phase is formed from a lithium-containing compound having a spinel crystal structure; the halite-like phase comprises at least one occupying element of Al, Nb, B, Si, F and S, and the occupying element occupies 16c or 8a vacancy of spinel octahedron or the position of oxygen ion in 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
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 rechargeable 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 terminal products such as mobile phones, notebook computers, tablet computers and the like. In recent years, electric vehicles have been rapidly developed under the push of governments and automobile manufacturers in various countries from the viewpoint of environmental protection, and lithium ion secondary batteries have become an ideal power source for a new generation of electric vehicles by virtue of their excellent performance. Currently, positive active materials of lithium ion secondary batteries that are of interest can be roughly classified into three categories: with lithium cobaltate (LiCoO)2) A layered material represented by lithium iron phosphate (LiFePO)4) Olivine-type material typified by lithium manganate (LiMn)2O4) Is a typical spinel structure material.
A spinel-structured high-voltage material is considered to be the most likely positive active material for the next-generation high-performance lithium battery as an advanced positive active material. In the circulating process of the high-voltage spinel cathode active material, because the traditional carbonate electrolyte interacts with the cathode active material, oxygen is lost on the surface of the cathode 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 cathode active material by doping elements, wherein the doping elements can form new chemical bonds in the material and on the surface so as to stabilize the crystal lattice oxygen on the bulk phase and the surface, but excessive doping of the bulk phase elements can reduce the capacity of the cathode active material and affect the electrochemical performance of the cathode active material.
Disclosure of Invention
Accordingly, there is a need for a modified cathode active material, a method for preparing the same, a cathode, and a lithium ion secondary battery, which can improve the structural stability of the cathode active material without sacrificing the electrochemical activity of the cathode active material.
The present invention provides a modified positive electrode active material comprising:
the primary particles comprise a spinel phase and a rock-salt-like phase, the primary particles are of a spinel octahedral structure, the spinel phase is an inner core, and the rock-salt-like phase is distributed on the surface of the spinel phase to form a shell;
the spinel phase is formed from a lithium-containing compound having a spinel crystal structure;
the halite-like phase comprises at least one occupying element of Al, Nb, B, Si, F and S, and the occupying element occupies 16c or 8a vacancy of spinel octahedron or the position of oxygen ion in 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 manganese lithium phosphate compound, and the lithium-containing compound has a chemical formula of Li1+xNi0.5-yMn1.5-zOuWherein x is more than or equal to 0.2 and less than or equal to 0.2, y is more than or equal to 0.2 and less than or equal to 0.2, z is more than or equal to 0.2 and u is more than or equal to 3.8 and less than or equal to 4.2.
In one embodiment, the spinel phase has a thickness of 0.1 μm to 30 μm.
In one embodiment, the thickness of the rock-salt-like phase is 0.5nm to 50 nm.
In one embodiment, the structure with the gradient distribution 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 contain one or more elements selected from 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 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 ℃ for 0.5-10 hours.
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 halite-like phase inducing agent is one or more of an oxide, a simple substance, a salt, and a compound of the placeholder element.
In one embodiment, the halite-like 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 to the rock-like salt phase inducer to 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:
the 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;
a separator and an electrolyte.
The primary particles of the modified cathode active material provided by the invention have a shell-core-like structure of a spinel phase core and a rock-salt-like phase shell, the rock-salt-like phase shell contains an occupying element, and the primary particles also contain a phosphorus element in gradient distribution. The structure is that a rock-salt-like phase shell containing an occupying element is constructed on the surface of an original electrode material, and due to the introduction of the occupying element, the occupying element induces the crystal structure on the surface of the original electrode material to generate phase change, so that the lattice constant of the surface of the original electrode material is changed, and the barrier of phosphorus doped into the electrode material structure is reduced, so that the phosphorus can be doped into the positive active material in a gradient distribution mode. The phosphorus element in gradient distribution relieves the structural stress generated in the process of lithium ion deintercalation, and reduces the reaction activity between the anode active material and the electrolyte. Meanwhile, the space occupying elements can further improve the electronic conductivity and the interface stability of the positive active material. The phosphorus element doped in a gradient manner and the occupying element in the rock-like salt phase can synergistically improve the stability of the surface structure of the positive active material, so that the capacity retention rate and the charging and discharging coulombic efficiency of the battery are improved. Meanwhile, each element in the plurality of occupied elements has a unique effect, the lattice constant can be stabilized for the aluminum element, the Taylor effect of the spinel structure is reduced, the long circulation of the lithium nickel manganese oxide is greatly benefited, the circulation can be improved for the niobium element, the niobium element can change the shape of the synthesized lithium nickel manganese oxide, and the shape, the particle size and the tap of the finally synthesized lithium nickel manganese oxide are effectively controlled. For nonmetallic elements of B, Si, F and S, the interface film containing the elements can be generated when the nonmetallic elements meet the electrolyte under high voltage, and the interface film containing the elements has higher rate performance and better stability.
Drawings
Fig. 1 is a STEM diagram of a modified positive electrode active material prepared in example 1;
fig. 2 is a STEM line scan of a modified positive active material prepared in example 1;
fig. 3 is a STEM graph of the surface of a modified positive active material prepared in example 2;
fig. 4 shows the relative content change of surface phosphorus element of the modified cathode active material prepared in example 2, which is characterized by XPS at different etching depths;
fig. 5 is a STEM graph of the surface of a modified positive active material prepared in example 3;
fig. 6 is an XPS chart of F element on the surface of the modified positive electrode active material prepared in example 4.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying 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 in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Other than as shown in the operating examples, or where otherwise indicated, 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, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be suitably varied by those skilled in the art utilizing the teachings disclosed herein to achieve the desired properties. The use of numerical ranges by endpoints includes all numbers within that range and any range within that range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, and the like.
A core-shell structure is generally defined as an ordered assembly of one material coated with another material by chemical bonding or other forces. The core-shell like structure "core" and "shell" as defined in the present invention are actually integral. The modified positive active material structure of the present invention includes two phases, resulting in a surface layer having a microstructure different from that of the interior of the material, the interior of the material thus formed being referred to as a "core", the surface layer being referred to as a "shell", and the material thus structured being defined as a material of a core-shell-like structure.
The "rock-salt-like phase" in the present invention 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 primary particles comprise a spinel phase and a rock-salt-like phase, the primary particles have a core-shell-like structure, the spinel phase is a core, and the rock-salt-like phase is distributed on the surface of the spinel phase to form an outer shell;
the spinel phase is formed of a lithium-containing compound having a spinel crystal structure including lithium, nickel and manganese,
the halite-like phase comprises at least one occupying element of Al, Nb, B, Si, F and S, and the occupying element occupies 16c or 8a vacancy of spinel octahedron or the position of oxygen ion in spinel octahedron;
the primary particles are doped with phosphorus elements, and the phosphorus elements are distributed in a gradient manner from outside to inside.
According to the modified cathode active material provided by the embodiment of the invention, the primary particles have a shell-core-like structure of a spinel phase core and a rock-salt-like phase shell, the rock-salt-like phase shell contains an occupying element, and the primary particles also contain a phosphorus element in gradient distribution. The structure is that a rock-salt-like phase shell containing an occupying element is constructed on the surface of an original electrode material, and due to the introduction of the occupying element, the occupying element induces the crystal structure on the surface of the original electrode material to generate phase change, so that the lattice constant of the surface of the original electrode material is changed, and the barrier of phosphorus doped into the electrode material structure is reduced, so that the phosphorus can be doped into the positive active material in a gradient distribution mode. The phosphorus element in gradient distribution relieves the structural stress generated in the process of lithium ion deintercalation, and reduces the reaction activity between the anode active material and the electrolyte. Meanwhile, the space occupying elements can further improve the electronic conductivity and the interface stability of the positive active material. The phosphorus element doped in a gradient manner and the occupying element in the rock-like salt phase can synergistically improve the stability of the surface structure of the positive active material, so that the capacity retention rate and the charging and discharging coulombic efficiency of the battery are improved.
The primary particle refers to a smallest unit constituting the positive electrode active material, and particularly refers to a smallest unit that can be determined based on the geometric configuration of appearance. Aggregates of primary particles are secondary particles. The primary particles have a core-shell-like structure in which a spinel phase core and a rock-salt-like phase shell are integrated, no grain boundary exists 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 manganese phosphate compound. More preferably, the lithium-containing compound may have a chemical formula of Li1+xNi0.5-yMn1.5-zOuWherein x is more than or equal to 0.2 and less than or equal to 0.2, y is more than or equal to 0.2 and less than or equal to 0.2, z is more than or equal to 0.2 and u is more than or equal to 3.8 and less than or equal to 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 formula may exhibit a spinel structure.
The preferred occupying element is Al, and the Al element is more favorable for improving the structural stability of the positive active material and reducing the barrier of doping phosphorus element into a spinel structure.
The spinel phase may have a thickness of any value between 0.1 μm and 30 μm, and may further 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 thickness of the rock-salt-like phase may be any value between 0.5nm and 50nm, and may 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, and 50 nm.
The modified positive active material provided by the invention is doped with phosphorus element, but is different from the phosphate-coated positive active material in the prior art. The phosphate-coated positive electrode active material is a material formed by covering a spinel positive electrode material with phosphate crystal structure or amorphous phosphate, and a coating layer can be seen on the surface of the material through a transmission electron microscope. In the modified cathode active material provided by the invention, phosphorus is doped in the primary particles, and the phosphorus is doped in the spinel structure in a gradient manner from the surface to the inside of the primary particle particles.
The spinel phase and the rock-salt-like phase of the primary particles are both doped with phosphorus, but the phosphorus is preferentially doped in the rock-salt-like phase. The doping amount of the phosphorus element in the primary particles is gradually reduced from outside to inside.
The structure in which the phosphorus element in the primary particles is distributed in a gradient manner may be defined as a phosphorus gradient doped layer, and the thickness of the phosphorus gradient doped layer may be any value between 0.5nm and 40nm, 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, 32nm, 35nm, and 38 nm.
The primary particles also contain one or more elements of magnesium, calcium, iron, copper, zinc, titanium, zirconium, cobalt, cadmium and vanadium.
The cathode material, the rock-like salt phase surface layer and the phosphorus gradient doped layer provided by the invention can be characterized by a characterization method commonly used in the field, for example, a Scanning Transmission Electron Microscope (STEM) and an X-ray photoelectron spectroscopy microscope (XPS) can be used for characterization, wherein the STEM can be used for accurately seeing that the surface of the cathode material occupies 16c octahedron 16c of spinel due to partial space occupying elementsOr the distribution of the rock-salt-like phase generated at the 8a position, STEM line scanning can also demonstrate the gradient distribution of the phosphorus element. Meanwhile, the gradient distribution of the phosphorus element in the phosphorus gradient doped layer can be proved by etching analysis of 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-Voltage balloon LiNi0.5Mn1.5O4 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 in Binding 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 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 a method known to those skilled in the art. For example, it can be prepared by a low-temperature solid phase method. Specifically, nickel salt, manganese salt, lithium hydroxide and oxalic acid can be mixed and ball-milled to prepare a precursor, 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 halite-like phase inducer may be one or more of an oxide, a simple substance, and a salt of the placeholder element. For example, Al2O3、Nb2O、Nb2O5、B2O3、SiO2、Al(OH)3、H3BO3、NaAlO2、Na2SiO3、NH4F. S and the like.
The halite-like phase inducing agent may also include one or more of organic or inorganic acids, 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 production of the rock-like salt phase.
The mass ratio of the phosphorus source to the rock salt-like phase inducer to the lithium-containing compound can be (1-30): (1-30): any ratio between 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-salt-like phase inducer, and the lithium-containing compound may be mixed by methods known to those skilled in the art, such as mechanical mixing, ultrasound, ball milling, and the like.
The sintering in step S30 may be performed in an oxygen, air, or inert atmosphere (such as nitrogen or argon) and an atmosphere containing oxygen. Preferably, the specific operation of the sintering process is as follows: heating to 600-1200 ℃ at a heating rate of 0.5-10 ℃/min, sintering for 0.5-10 h, and cooling to room temperature at a cooling rate of 0.5-10 ℃/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 member formed of a highly conductive metal as used in a positive electrode of a 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, since it may vary depending on the shape of the lithium ion secondary battery, etc. For example, the positive electrode collector may have various shapes such as a rod shape, a plate shape, a sheet shape, and a foil shape.
The positive active material layer further includes a conductive additive and a binder.
The conductive additive may be a conductive additive that is 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 thereto, and may be composed of polyvinylidene fluoride (PVDF), or 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:
the 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;
a separator and an electrolyte.
As a current collector of the negative electrode,
the negative electrode, separator and electrolyte may employ negative electrode current collectors, separators and electrolyte materials that are 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 rod-shaped, plate-shaped, sheet-shaped, and foil-shaped, and may vary depending on the shape of the lithium ion secondary battery, and the like. The negative active material layer includes a negative active material, a conductive additive, and a binder. The negative active material, conductive additive and binder are also conventional in the art. In some embodiments, the negative active material is lithium metal. The conductive additives and binders are as described above and will not be described in detail here.
The separator may be a separator used in a general lithium ion secondary battery, and examples thereof include a microporous film made of polyethylene or polypropylene; a multi-layer film of a porous polyethylene film and polypropylene; nonwoven fabrics formed of polyester fibers, aramid fibers, glass fibers, and the like; and a base film formed by adhering ceramic fine particles such as silica, alumina, and titania to the surfaces thereof. In some embodiments, the separator is a three layer film of PP/PE/PP coated on both sides with alumina.
The electrolyte may include an electrolyte and a non-aqueous organic solvent. The electrolyte is preferably LiPF6、LiBF4、LiSbF6、LiAsF6. The non-aqueous organic solvent may be carbonates, esters and ethers. Among them, carbonates such as Ethylene Carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC) and ethylmethyl carbonate (EMC) can be preferably used.
The following are specific examples, which are intended to provide further detailed description of the present invention and to assist those skilled in the art and researchers in understanding the present invention, and the technical conditions and the like are not intended to limit the present invention. 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 Spectroscopy (XPS) an ESCALB 250 model X-ray photoelectron spectrometer manufactured by Thermo Fisher corporation was used to study the types of surface elements and chemical environments of powder samples, wherein the X-ray radiation source was Mg K α.
Example 1
9g of LiNi0.5Mn1.5O4Material, 0.05g B2O3And 0.1g (NH)4)2HPO4And uniformly mixing, calcining the obtained mixture in oxygen at 600 ℃ for 5h, wherein the heating rate is 3 ℃/min, and the cooling rate is 5 ℃/min, so as to obtain the modified anode active material.
Fig. 1 shows a STEM diagram of a modified positive electrode active material prepared in example 1. As can be seen from the STEM diagram of the modified cathode active material of fig. 1, the surface of the material has a rock-salt-like phase generated by occupying 16c atoms of spinel octahedron, and the thickness of the rock-salt-like phase is about 10 nm.
Fig. 2 is a STEM line scan of the phosphorus content on the surface of the modified cathode active material prepared in example 1, and it can be seen from fig. 2 that there is no coating layer on the surface of doped lithium nickel manganese oxide, and it can be seen from fig. 1 that the phosphorus element is distributed in the rock-like salt phase, and the content of the phosphorus element gradually decreases from the surface to the inside.
Example 2
9g of LiNi0.4Mn1.6O4Material, 0.2g H3PO4And 0.267g Nb2O5And uniformly mixing, calcining the obtained mixture in oxygen at 800 ℃ for 5h, wherein the heating rate is 3 ℃/min, and the cooling rate is 5 ℃/min, so as to obtain the modified anode active material.
Fig. 3 shows a STEM diagram of a modified positive electrode active material prepared in example 2. As can be seen from the figure, the surface of the material has a spinel octahedral 8a atom occupying rock-like salt phase, and the thickness of the rock-like salt phase is about 5 nm.
Fig. 4 shows the relative content change of the phosphorus element on the surface of the modified cathode active material prepared in example 2, which is characterized by XPS at different etching depths, and we can see that the content of the phosphorus element is continuously reduced from the surface to the inside along with the increase of the etching depth.
Example 3
9g of LiNi0.4Mn1.6O4Material, 0.1g SiO2And 0.133g (NH)4)2HPO4And 20ml of deionized water were added to the beaker and mixed uniformly, and the beaker was placed in an oil bath pan at 120 ℃ and heated with stirring for 5 hours to obtain a dry mixture. And calcining the obtained mixture in oxygen at 850 ℃ for 5h, wherein the heating rate is 3 ℃/min, and the cooling rate is 5 ℃/min, so as to obtain the modified positive active material.
Fig. 5 shows a STEM graph of the modified positive active material prepared in example 3. As can be seen from the figure, the surface of the material has 2-3 nm spinel octahedron 8a and 16c atom occupied rock-salt-like phase, and the thickness of the surface rock-salt-like phase is about 2 nm.
Example 4
9g of LiNi0.4Mn1.6O4Material, 0.2g H3PO4And 0.267g NH4And F, uniformly mixing, calcining the obtained mixture in oxygen at 800 ℃ for 5h, 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 an XPS spectrum of the modified cathode active material prepared in example 4, and indicates that the surface of the material contains F element.
Example 5
9g of LiNi0.5Mn1.5O4Material, 0.03g Al2O3And 0.125g (NH)4)2HPO4And uniformly mixing, calcining the obtained mixture in air at 800 ℃ for 5h, 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 LiNi0.5Mn1.5O4Material, 0.015g S and 0.15g (NH)4)2HPO4And uniformly mixing, calcining the obtained mixture in a closed space at 825 ℃ for 5h, wherein the heating rate is 3 ℃/min, and the cooling rate is 5 ℃/min, so as to obtain the modified anode active material.
Comparative example 1
Essentially the same procedure as in example 1, except that no phosphorus source (NH) was added4)2HPO4。
Comparative example 2
The preparation method is basically the same as that of example 1, except that the rock-like salt phase inducer B2O3Hydrochloric acid is replaced.
Performance testing
The positive electrode active materials prepared in examples 1 to 4 and comparative examples 1 to 2 were assembled into a button cell according to the following procedure.
(1) Preparation of Positive electrode sheet
The positive electrode active material prepared in the examples, carbon black as a conductive additive, and polyvinylidene fluoride (PVDF) as a conductive additiveAnd the binder is dispersed in N-methyl pyrrolidone (NMP) according to the weight ratio of 80:10:10, and is uniformly mixed to prepare uniform anode slurry. Uniformly coating the uniform positive electrode slurry on an aluminum foil current collector with the thickness of 15 mu m, drying at 55 ℃ to form a pole piece with the thickness of 100 mu m, and rolling the pole piece under a roller press (the pressure is about 1MPa multiplied by 1.5 cm)2) Cut into the diameter of
Then the round piece is placed in a vacuum oven to be dried for 6 hours at the temperature of 120 ℃, and after natural cooling, the round piece is taken out and placed in a glove box to be used as a positive pole piece.
(2) Assembling lithium ion secondary battery
And (2) in a glove box filled with inert atmosphere, taking metal lithium as the negative electrode of the battery, taking a PP/PE/PP three-layer film with two sides coated with alumina as a diaphragm, putting the diaphragm between the positive electrode and the negative electrode, dropwise adding common carbonate electrolyte, taking the positive electrode piece prepared in the step (1) as the positive electrode, and assembling into the button battery with the model number of CR 2032.
High-temperature cycle test:
and standing the prepared button cell for 10 hours at room temperature (25 ℃), then carrying out charge-discharge activation on the button cell, and then carrying out charge-discharge cycle test on the prepared button cell by adopting a blue cell charge-discharge tester. The method comprises the steps of firstly cycling at a rate of 0.1C for 1 week under the condition of room temperature (25 ℃), and then continuing cycling at a rate of 0.2C for 4 weeks, wherein the charging and discharging voltage range of the battery is controlled to be 3.5V-4.9V. Then, the button cell is transferred to a high-temperature environment of 55 ℃, the circulation is continued for 50 weeks at the multiplying power of 0.2C, and the charging and discharging voltage range of the cell is still controlled to be 3.5V-4.9V.
With LiNi0.5Mn1.5O4、LiNi0.4Mn1.6O4As a control, the measured data are shown in Table 1.
TABLE 1 electrochemical Properties of Positive electrode active Material of examples of the present invention
The results showed that the original LiNi0.5Mn1.5O4Material, pristine LiNi0.4Mn1.6O4Materials and positive active materials prepared in comparative example 1 and comparative example 2 were assembled into a battery, which shows a rapid capacity fade after 50 weeks in a high temperature test environment of 55 ℃, due to decomposition of the electrolyte and dissolution of Mn/Ni of the positive active material, resulting in a rapid capacity fade of the materials; the capacity of the material subjected to gradient doping of P prepared in examples 1-4 is hardly attenuated after 50 weeks in a high-temperature test environment at 55 ℃, and harmful side reactions between the positive active material and the electrolyte are relieved, and the decomposition of the electrolyte and the dissolution of Mn/Ni are inhibited, so that the cycling stability of the battery is improved.
The above table shows that after phosphorus doping and surface modification of the placeholder elements (Al, Nb, B, Si, F, S), harmful side reactions between the positive active material and the electrolyte are alleviated, and decomposition of the electrolyte and dissolution of the positive active material Mn/Ni are inhibited, thereby improving the cycling stability of the battery. Meanwhile, gradient phosphorus doping and occupying elements (Al, Nb, B, Si, F and S) have synergistic effect, and compared with single phosphorus doping and occupying element (Al, Nb, B, Si, F and S) surface modification, the material modified by the two elements together has obviously improved cycling stability.
With LiNi0.5Mn1.5O4As a control, the measured electrochemical data are listed in table 2.
TABLE 2 electrochemical rate Performance of the cathode active materials of the examples of the present invention
The above table shows that the rate capability of the lithium nickel manganese oxide material is increased on the surface of the material through the non-metal element such as boron element.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (13)
1. A modified positive electrode active material, comprising:
the primary particles comprise a spinel phase and a rock-salt-like phase, the spinel phase is a core, and the rock-salt-like phase is distributed on the surface of the spinel phase to form a shell;
the spinel phase is formed from a lithium-containing compound having a spinel crystal structure;
the halite-like phase comprises at least one occupying element of Al, Nb, B, Si, F and S, and the occupying element occupies 16c or 8a vacancy of spinel octahedron or the position of oxygen ion in 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 manganese phosphateA lithium compound having the chemical formula Li1+xNi0.5-yMn1.5-zOuWherein x is more than or equal to 0.2 and less than or equal to 0.2, y is more than or equal to 0.2 and less than or equal to 0.2, z is more than or equal to 0.2 and u is more than or equal to 3.8 and less than or equal to 4.2.
3. The modified cathode active material according to claim 1, wherein the spinel phase has a thickness of 0.1 to 30 μm.
4. The modified positive electrode active material according to claim 1, wherein the thickness of the rock-salt-like phase is 0.5nm to 50 nm.
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 40 nm.
6. The modified positive electrode active material according to claim 1, wherein the primary particles further contain one or more elements selected from the group consisting of magnesium, calcium, iron, copper, zinc, titanium, zirconium, cobalt, cadmium and vanadium.
7. A method for preparing a 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 the heating rate of 0.5-10 ℃/min, sintering for 0.5-10 hours, and cooling to room temperature at the cooling rate of 0.5-10 ℃/min.
8. The method for producing a modified positive electrode active material according to claim 7, wherein the phosphorus source includes 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 for preparing a modified cathode active material according to claim 7, wherein the rock-salt-like phase inducer is one or more of an oxide, a simple substance, and a salt of the space-occupying element.
10. The method of claim 9, 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.
11. The method for preparing the modified cathode active material according to any one of claims 7 to 10, wherein the mass ratio of the phosphorus source, the rock salt-like phase inducer and the lithium-containing compound is (1 to 30): (1-30): 2000.
12. a positive electrode of a lithium ion secondary battery, comprising a positive electrode current collector and a positive electrode active material layer on the positive electrode current collector, wherein the positive electrode active material layer comprises the modified positive electrode active material according to claims 1 to 6.
13. A lithium-ion secondary battery characterized by comprising:
a positive electrode according to claim 12;
a negative electrode including a negative electrode current collector and a negative electrode active material layer on the negative electrode current collector;
a separator and an electrolyte.
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| 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 |
| CN116885156A (en) * | 2023-09-07 | 2023-10-13 | 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 |
| CN117080535A (en) * | 2023-10-19 | 2023-11-17 | 中创新航科技集团股份有限公司 | Cylindrical battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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| 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 |
Cited By (5)
| 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 |
| CN116885156A (en) * | 2023-09-07 | 2023-10-13 | 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 |
| 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 |
| CN117080535A (en) * | 2023-10-19 | 2023-11-17 | 中创新航科技集团股份有限公司 | Cylindrical battery |
| CN117080535B (en) * | 2023-10-19 | 2023-12-22 | 中创新航科技集团股份有限公司 | Cylindrical battery |
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