CN110660978A - Lithium ion battery positive electrode material with core-shell structure and preparation method thereof, positive plate, lithium ion battery and application thereof - Google Patents

Lithium ion battery positive electrode material with core-shell structure and preparation method thereof, positive plate, lithium ion battery and application thereof Download PDF

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Publication number
CN110660978A
CN110660978A CN201910810717.5A CN201910810717A CN110660978A CN 110660978 A CN110660978 A CN 110660978A CN 201910810717 A CN201910810717 A CN 201910810717A CN 110660978 A CN110660978 A CN 110660978A
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source
lithium
positive electrode
shell structure
temperature
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CN110660978B (en
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熊得军
王大为
张舒
J·W·江
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Farasis Energy Ganzhou Co Ltd
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Farasis Energy Ganzhou Co Ltd
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Priority to PCT/CN2020/112605 priority patent/WO2021037267A1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to the field of lithium batteries, and provides a lithium ion battery anode material with a core-shell structure and a preparation method thereofβRAO4(ii) a The core structure of the anode material is composed of a ternary composite anode material, and the structural formula of the ternary composite anode material is LiαNixCoyM1‑y‑xO2R is selected from Mn and/or Fe, A is P and/or Si, and M is Mn and/or Al. The invention provides a positive plate, a lithium ion battery and application thereof. Hair brushThe shell structure material of the lithium ion battery composite positive electrode material with the core-shell structure is an iron-based polyanionic lithium salt, the microcosmic crystal structure is very stable, octahedral vacancies and tetrahedral vacancies in the crystal structure provide a large number of channels for lithium ions to shuttle, the material can still ensure the stability of the material at 600 ℃, and the safety performance of the battery is good in the using process.

Description

Lithium ion battery positive electrode material with core-shell structure and preparation method thereof, positive plate, lithium ion battery and application thereof
Technical Field
The invention relates to a lithium ion battery anode material with a core-shell structure, a preparation method thereof, an anode plate, a lithium ion battery and application thereof in new energy automobiles.
Background
The ternary cathode material is the most widely applied cathode material in the market of pure electric passenger vehicles of new energy automobiles at present, has the excellent performance characteristics of high energy density, high platform voltage, long cycle life, high and low temperature performance and the like, and can meet the core requirements of new energy passenger vehicles on driving range, high energy consumption ratio, quick charging and the like. Due to the influence of the preparation process, the pH value of the ternary cathode material is higher (more than 10), and LiCO is remained on the surface3And alkaline lithium salt substances such as LiOH and the like, and the content of residual alkaline lithium salt is increased by times along with the increase of the content of nickel in the ternary cathode material.
During battery cycling, the residual alkaline lithium salt reacts with the LiPF in the electrolyte6The reaction occurs to form gas, which not only changes the composition of the electrolyte to affect the cycle life of the battery, but also affects the storage life of the battery due to the presence of the gas. The existing anode material manufacturers mainly adopt a coprecipitation method to deposit and coat a layer of metal oxide (such as Al) on the surface of the material2O3、MgO、ZrO2Etc.) to form a core-shell structure, and prevent the ternary material from directly contacting with the electrolyte through a metal oxide layer on the surface, thereby improving the cycle life and the storage life.
Disclosure of Invention
The invention aims to solve the problems of reducing or eliminating the influence of alkaline lithium salt substances left on the surface of the ternary cathode material on the electrolyte and prolonging the cycle life and the storage life of the battery.
The invention also aims to solve the problems of ion shuttle transmission when lithium ions are extracted from and inserted into the lithium ion battery composite anode material with the core-shell structure, improve the polarization internal resistance of the anode, reduce the internal resistance of the battery and optimize the thermal characteristics of the battery.
Research suggests that a coprecipitation method adopted in the prior art can coat a layer of metal oxide on the surface of a material, and can improve the performance of a ternary cathode material to a certain extent, but some problems still can affect the performance of a battery:
1. the metal oxide coating layer prepared by the coprecipitation method cannot solve the problem of residual lithium salt substances on the surface of the ternary cathode material, and is only coated in the shell structure. In the recycling process, once the shell structure is damaged, the shell structure can still be contacted with the electrolyte and react, and the cycle life and the storage life of the battery are influenced.
2. The metal oxide coating layer can prevent the electrolyte from directly contacting with the ternary cathode material to a certain extent, but the metal oxide coating layer does not have a lithium ion shuttling channel, and the lithium ions in the cathode need to be shuttled and transmitted from the gaps of the metal oxide coating layer in the process of extraction and insertion. The coating layer is required to be compact in order to prevent the electrolyte from permeating, so that the shuttle transmission of lithium ions is difficult, the polarization internal resistance of the anode is increased, and the internal resistance and the thermal characteristic of the battery are macroscopically influenced.
To improve the technical status and achieve the aforementioned object, according to an aspect of the present invention, a positive electrode material of a lithium ion battery with a core-shell structure is provided, wherein the shell structure of the positive electrode material is composed of polyanion lithium salt with chemical formula of LiβRAO4(ii) a The core structure of the anode material is composed of a ternary composite anode material, and the structural formula of the ternary composite anode material is LiαNixCoyM1-y-xO2Wherein R is selected from Mn and/or Fe, A is P and/or Si, and M is Mn and/or Al.
According to a second aspect of the present invention, there is provided a method for preparing the positive electrode material according to the present invention, the method comprising:
(1) weighing a lithium source, an R compound source, an A compound source and a carbon source according to a metered molar ratio, and adding the lithium source, the R compound source, the A compound source and the carbon source into a solvent;
(2) stirring and dispersing the mixture in the step (1) under a closed condition to form sol;
(3) At normal temperature, the ternary cathode material LiαNixCoyM1-y-xO2Adding the mixture into the sol obtained in the step (2), and stirring and mixing to obtain a mixed solution;
(4) heating the mixed solution in the step (3) to a temperature lower than 100 ℃, stirring, and carrying out saturated precipitation to form microgel;
(5) sending the microgel obtained in the step (4) into a spray dryer for spray drying to form a core-shell structure with uniform particle size and a gel-coated surface of the ternary cathode material, wherein the thickness of the coating layer is 50-100 nm;
(6) and (3) under a reducing atmosphere, at the temperature of 500-800 ℃, putting the gel core-shell structure material coated by the ternary cathode material formed in the step (5) into a high-temperature reaction kettle for reduction, and then cooling and screening.
According to a third aspect of the present invention, the present invention provides a positive electrode sheet comprising a positive electrode current collector and a positive electrode active material layer coated on the positive electrode current collector, wherein the positive electrode active material of the positive electrode active material layer is partially or completely derived from the positive electrode material of the present invention.
According to a fourth aspect of the present invention, there is provided a lithium ion battery comprising: the lithium battery comprises a positive plate, a negative plate, a diaphragm, electrolyte, a positive tab, a negative tab and an aluminum plastic film, wherein the positive plate is the positive plate disclosed by the invention.
Through the technical scheme, the invention has the following technical effects:
1. in the lithium ion battery composite anode material with the core-shell structure, alkaline lithium salt substances remained on the surface can be consumed as lithium source reactants in the process of forming the shell structure. The reason is presumably that the main component of the basic lithium salt substance remaining on the surface is lithium carbonate and/or lithium hydroxide, which can serve as a lithium source in the reactant forming the polyanionic lithium salt.
2. The shell structure material of the lithium ion battery composite anode material with the core-shell structure provided by the invention is polyanionic lithium salt, the microcosmic crystal structure is very stable, octahedral vacancies and tetrahedral vacancies in the crystal structure provide a large number of channels for lithium ions to shuttle, the material can still ensure the stability of the material at 600 ℃, and the safety performance of the battery is good in the using process.
3. According to the lithium ion battery composite anode material with the core-shell structure, the shell structure is prepared by the specific sol-gel method, the surface coating layer is more compact and uniform, and the thickness of the coating layer is thinner. Presumably, the sol solution can be uniformly dispersed on a molecular scale to form a uniform and stable phase, the gel is saturated and precipitated to be tightly and uniformly coated on the surface of the core structure in the process of evaporating the solvent to form the gel, and the thickness of the coating can be controlled by controlling the precipitation rate and time of the gel.
In the present invention, polyanionic lithium salt LiβRAO4As the anode material, the lithium ion battery has an olivine or spinel structure with stable structure, lithium ions can be freely extracted and inserted, the safety performance and the cycle life are good, and the defect is that the energy density is low; ternary composite positive electrode material LiαNixCoyM1-y-xO2The composite material has the characteristic of high energy density, especially when x is more than or equal to 0.7, the energy density can reach 270Wh/kg, but the thermal stability, safety performance and cycle performance of the material are poor, and the two materials can be compounded to combine the advantages of the two materials, so that the respective defects are overcome.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a lithium ion battery anode material with a core-shell structure, wherein the shell structure of the anode material is polyanion lithium salt with a chemical formula of LiβRAO4(ii) a The core structure of the anode material is composed of a ternary composite anode material, and the structural formula of the ternary composite anode material is shown in the specificationLiαNixCoyM1-y-xO2Wherein R is selected from Mn and/or Fe, A is P and/or Si, and M is Mn and/or Al.
The lithium ion battery with the core-shell structure is characterized in that a ternary anode material is used as a core, and polyanion lithium salt is coated on the surface of the ternary anode material to form the core-shell structure of the shell.
The shell structure material of the lithium ion battery composite anode material with the core-shell structure provided by the invention is polyanionic lithium salt, the microcosmic crystal structure is very stable, octahedral vacancies and tetrahedral vacancies in the crystal structure provide a large number of channels for lithium ions to shuttle, the material can still ensure the stability of the material at 600 ℃, and the safety performance of the battery is good in the using process.
According to a preferred embodiment of the present invention, β is in the range of 0.8 to 2.
According to a preferred embodiment of the present invention, α is in the range of 0.5 to 1.2.
According to a preferred embodiment of the present invention, x and y range from 0 to 1, and x + y < 1.
According to the lithium ion battery composite anode material with the core-shell structure, the shell structure provides a lithium ion shuttle transmission channel, so that the reduction of the internal resistance of the battery is facilitated, and the thermal characteristic of the battery is optimized.
The object of the present invention can be achieved by a positive electrode material having the above structure and composition, and the present invention particularly provides a method for preparing the positive electrode material of the present invention, the method comprising:
(1) weighing a lithium source, an R compound source, an A compound source and a carbon source according to a metered molar ratio, and adding the lithium source, the R compound source, the A compound source and the carbon source into a solvent;
(2) stirring and dispersing the mixture in the step (1) under a closed condition to form sol;
(3) at normal temperature, the ternary cathode material LiαNixCoyM1-y-xO2Adding the mixture into the sol obtained in the step (2), and stirring and mixing to obtain a mixed solution;
(4) heating the mixed solution in the step (3) to a temperature lower than 100 ℃, stirring, and carrying out saturated precipitation to form microgel;
(5) sending the microgel obtained in the step (4) into a spray dryer for spray drying to form a core-shell structure with uniform particle size and a gel-coated surface of the ternary cathode material, wherein the thickness of the coating layer is 50-100 nm;
(6) and (3) under a reducing atmosphere, at the temperature of 500-800 ℃, putting the gel core-shell structure material coated by the ternary cathode material formed in the step (5) into a high-temperature reaction kettle for reduction, and then cooling and screening.
Preferably, the method of the invention comprises:
(1) weighing a lithium source, an R compound source, an A compound source and a carbon source according to a metered molar ratio, and adding the lithium source, the R compound source, the A compound source and the carbon source into a solvent;
(2) stirring and dispersing the mixture in the step (1) under a closed condition to form sol, wherein the dispersion speed is set to be 500-1500r/min, and the stirring time is set to be 0.5-8 hr;
(3) at normal temperature, the ternary cathode material LiαNixCoyM1-y-xO2Adding into the sol in the step (2), stirring and mixing to obtain a mixed solution, wherein the stirring speed is set to be 500-1500r/min, and the stirring time is set to be 0.5-8 hr;
(4) heating the mixed solution in the step (3) to a temperature lower than 100 ℃, stirring the mixed solution with solvent volatilization, setting the stirring speed at 200-300r/min and the stirring time at 1-12hr, and forming microgel by sol saturation and precipitation;
(5) sending the microgel obtained in the step (4) into a spray dryer for spray drying to form a core-shell structure with uniform particle size and a gel-coated surface of the ternary cathode material, wherein the thickness of the coating layer is 50-100 nm;
(6) and (3) under a reducing atmosphere, at the temperature of 500-800 ℃, putting the gel core-shell structure material coated by the ternary cathode material formed in the step (5) into a high-temperature reaction kettle for reduction for 2-12 hours, and then cooling and screening.
The lithium ion battery composite anode material with the core-shell structure is prepared by adopting the sol-gel method to obtain a shell structure coating layer, the coating layer formed by gel is uniform and compact, the microstructure size reaches the nanometer level, the surface of the ternary anode material is completely coated, and the thickness of the coating layer can reach below 1 um.
According to the lithium ion battery composite positive electrode material with the core-shell structure, alkaline lithium salt substances remained on the surface of the ternary positive electrode material can be used as a lithium source reactant to participate in the preparation reaction process of the shell structure, the alkaline lithium salt substances remained on the surface of the ternary positive electrode material can be effectively reduced or removed, and the influence of the alkaline lithium salt substances on the cycle life and the storage life of the battery is reduced or eliminated.
According to the method provided by the invention, the lithium source used for preparing the sol-gel by the shell structure of the lithium ion battery composite cathode material with the core-shell structure is preferably one or more of lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate and lithium citrate.
According to the method of the present invention, it is preferable that the source of the R compound is one or more of the iron source and the manganese source.
According to the process of the present invention, it is preferred that the source of the a compound is one or more of the phosphorus source and the silicon source.
According to the method provided by the invention, the iron source used for preparing the sol-gel by the shell structure of the lithium ion battery composite cathode material with the core-shell structure is preferably one or more of ferrous oxalate, ferrous acetate, ferric phosphate and ferric oxide.
According to the method, the manganese source used for preparing the sol-gel with the shell structure of the lithium ion battery composite cathode material with the core-shell structure is preferably one or more of manganese sulfate, manganese dioxide and manganese carbonate.
According to the method provided by the invention, the phosphorus source used for preparing the sol-gel by the shell structure of the lithium ion battery composite cathode material with the core-shell structure is preferably one or more of ammonium dihydrogen phosphate, ammonium hydrogen phosphate and ammonium phosphate.
According to the method provided by the invention, the silicon source used for preparing the sol-gel by the shell structure of the lithium ion battery composite cathode material with the core-shell structure is preferably tetraethoxysilane and/or methyl orthosilicate.
According to the method, the carbon source used for preparing the sol-gel by the shell structure of the lithium ion battery composite cathode material with the core-shell structure is preferably one or more of glucose, sucrose and carbon black.
According to the method, the solvent used for preparing the sol-gel with the shell structure of the lithium ion battery composite cathode material with the core-shell structure is preferably one or more of acetone, diethyl ether and absolute ethyl alcohol.
According to the method, the ternary positive electrode material is preferably LiNi0.8Co0.1Mn0.1O2、LiNi0.83Co0.11Mn0.06O2、LiNi0.8Co0.1Al0.1O2、LiNi0.6Co0.2Mn0.2O2And LiNi0.5Co0.3Mn0.2O2One or more of (a).
The cathode material prepared by the method has the structure and the composition of the cathode material, and the surface coating layer of the cathode material prepared by the method is more compact and uniform, and the thickness of the coating layer is thinner.
According to the process of the present invention, it is preferred that the molar ratio of Li and C of the lithium source to the carbon source in step (1) is 4-5: 1.
According to the method of the present invention, in the step (2), the stirring speed is preferably 900-1100r/min, and the stirring time is preferably 5-6 hr.
According to the method of the present invention, in the step (3), the stirring speed is preferably set to 900-1100r/min, and the stirring time is preferably 2-3 hr.
According to the method of the present invention, it is preferable that in the step (4), the temperature is 60 to 100 ℃, preferably 80 to 95 ℃, and the stirring time is set to 2.5 to 4.5 hr.
According to the method of the present invention, in the preferred step (5), the spray drying conditions include a feeding temperature of 150-.
According to the method of the present invention, in the preferable step (6), the reducing conditions include: the temperature is 600 ℃ and 650 ℃, and the time is 6-8 hr.
According to the method of the present invention, preferably, the reducing gas is one or more of carbon monoxide, hydrogen and a mixed gas of nitrogen and hydrogen.
According to the method of the present invention, the present inventors have found that the performance of the positive electrode material of the present invention can be improved by reducing according to the following steps, and with respect to the present invention, it is preferable that the step of reducing comprises:
under the condition of nitrogen-hydrogen mixed gas, preferably selecting the volume ratio of nitrogen to hydrogen (3:7) - (6:4), heating to 200-300 ℃ at the heating rate of 1-5 ℃/min, and carrying out heat preservation for 4-6 h; continuously heating to 400-500 ℃ at the heating rate of 1-5 ℃/min and keeping the temperature for 2-4hr in the presence of nitrogen-hydrogen mixed gas, preferably in the volume ratio of nitrogen to hydrogen (3:7) - (6: 4); finally, under the hydrogen atmosphere, the temperature is raised to 600-800 ℃ at the temperature raising rate of 1-5 ℃/min, preferably to 600-650 ℃, and the heat preservation time is 2-12hr, preferably to 6-8 hr.
According to the invention, preferred cooling conditions include: introducing argon gas for protection, cooling to 150 ℃ and 250 ℃ at the speed of 0.1-0.5 ℃/min, stopping introducing protective gas argon gas, and cooling to room temperature at the speed of 2-5 ℃/min.
The invention provides a positive plate, which comprises a positive current collector and a positive active material layer coated on the positive current collector, wherein the positive active material of the positive active material layer is partially or completely derived from the positive material.
The present invention provides a lithium ion battery, comprising: the lithium battery comprises a positive plate, a negative plate, a diaphragm, electrolyte, a positive tab, a negative tab and an aluminum plastic film, wherein the positive plate is the positive plate disclosed by the invention.
The invention provides application of the lithium ion battery in a new energy automobile.
The preparation method of the lithium ion battery composite anode material with the core-shell structure has the performance characteristics that alkaline lithium salt substances remained on the surface of the ternary anode material can be consumed as reactants in the preparation process of the material, and the influence of the alkaline lithium salt substances on the cycle and storage performance of the battery is effectively avoided.
The core-shell structure provided by the invention can ensure that the ternary cathode material has a stable structure, and can ensure that lithium ions can rapidly shuttle through the core-shell structure, so that the internal resistance of the battery is reduced, and the thermal characteristics of the battery are optimized.
According to the lithium ion battery composite anode material with the core-shell structure, the shell structure is formed by adopting a sol-gel method, the surface coating layer is more uniform and compact, and the coating thickness is thinner.
Example 1
1. Weighing LiCO as lithium source in a certain molar ratio3FeC as iron source2O4Phosphorus source (NH)4)H2PO4Adding a carbon source glucose into an acetone solvent, wherein the ratio of Li: fe: p: the molar ratio of C is 0.99:1: 0.2, and the solid-to-liquid ratio is 1: 40.
2. And (3) stirring and dispersing the mixture in the step (1) under a closed condition to form sol, wherein the dispersion rotating speed is set to be 1000r/min, and the stirring time is set to be 5.5 hr.
3. A certain amount of ternary cathode material LiNi is added0.83Co0.11Mn0.06O2Adding into the sol solution of step 2, stirring at 1000r/min for 2.5 hr.
4. And (3) stirring the mixed solution in the step (3) at a temperature of 90 ℃ while volatilizing the solvent, wherein the stirring speed is set to 250r/min, the stirring time is set to 3.5hr, the solvent is evaporated at a high temperature, and the sol is saturated and precipitated to form the microgel.
5. And (4) feeding the microgel mixed solution obtained in the step (4) into a spray dryer, setting the feeding temperature to be 250 ℃, the discharging temperature to be 90 ℃ and the rotational speed of an atomizer to be 20000rpm, so as to form a core-shell structure with the surface of the ternary cathode material being uniform in particle size and coated with gel, wherein the thickness of the coating layer is 50-100 nm.
6. And (3) coating the gel particles with the ternary cathode material formed in the step (5), putting the gel particles into a high-temperature reaction kettle, wherein the volume ratio of nitrogen to hydrogen is 5:5, heating to 250 ℃ at a heating rate of 3 ℃/min, and keeping the temperature for 5 hours; continuously heating to 500 deg.C at a speed of 2 deg.C/min for 3hr in the presence of nitrogen-hydrogen mixture at a volume ratio of nitrogen to hydrogen of 5: 5; continuously heating to 650 deg.C at 1 deg.C/min under hydrogen atmosphere, and maintaining for 8 hr.
7. And (3) introducing argon gas for protection into the particles in the step (6) in a high-temperature reaction kettle, cooling to 200 ℃ at the speed of 0.1 ℃/min, stopping introducing the protective gas of argon gas, cooling to room temperature at the speed of 5 ℃/min, cooling and screening to obtain the lithium ion battery composite anode material with the core-shell structure (the shell structure of the anode material is polyanionic lithium salt, and the chemical formula of the polyanionic lithium salt is LiFePO)4(ii) a The core structure of the anode material is composed of a ternary composite anode material, and the structural formula of the ternary composite anode material is LiNi0.83Co0.11Mn0.06O2)。
Example 2
1. Weighing LiOH as a lithium source and Fe (COOCH) as an iron source according to a certain metering molar ratio3)2Adding a silicon source TEOS and a carbon source sucrose into a certain amount of acetone solvent, wherein the ratio of Li: fe: si: the molar ratio of C is 1.98:1: 0.25, and the solid-to-liquid ratio is 1: 40.
2. And (3) stirring and dispersing the mixture in the step (1) under a closed condition to form sol, wherein the dispersion rotating speed is set to be 1000r/min, and the stirring time is set to be 5.5 hr.
3. A certain amount of ternary cathode material LiNi is added0.83Co0.11Mn0.06O2Adding into the sol solution of step 2, stirring at 1000r/min for 2.5 hr.
4. And (3) stirring the mixed solution in the step (3) at a temperature of 90 ℃ while volatilizing the solvent, wherein the stirring speed is set to 250r/min, the stirring time is set to 3.5hr, the solvent is evaporated at a high temperature, and the sol is saturated and precipitated to form the microgel.
5. And (4) feeding the microgel mixed solution obtained in the step (4) into a spray dryer, setting the feeding temperature to be 250 ℃, the discharging temperature to be 90 ℃ and the rotational speed of an atomizer to be 20000rpm, so as to form a core-shell structure with the surface of the ternary cathode material being uniform in particle size and coated with gel, wherein the thickness of the coating layer is 50-100 nm.
6. Coating the ternary cathode material formed in the step (5) with gel particles, putting the gel particles into a high-temperature reaction kettle, heating the ternary cathode material to 250 ℃ at a heating rate of 3 ℃/min for heat preservation for 5 hours under the condition of nitrogen-hydrogen mixed gas with a volume ratio of nitrogen to hydrogen of 5: 5; continuously heating to 500 deg.C at a speed of 2 deg.C/min for 3hr in the presence of nitrogen-hydrogen mixture at a volume ratio of nitrogen to hydrogen of 5: 5; continuously heating to 650 deg.C at 1 deg.C/min under hydrogen atmosphere, and maintaining for 8 hr.
7. And (3) introducing argon gas for protection into the particles in the step (6) in a high-temperature reaction kettle, cooling to 150 ℃ at the speed of 0.3 ℃/min, stopping introducing protective gas argon gas, cooling to room temperature at the speed of 2 ℃/min, cooling and screening to obtain the lithium ion battery composite positive electrode material with the core-shell structure, wherein the shell structure of the positive electrode material consists of polyanion lithium salt, and the chemical formula of the polyanion lithium salt is Li2FeSiO4(ii) a The core structure of the anode material is composed of a ternary composite anode material, and the structural formula of the ternary composite anode material is LiNi0.83Co0.11Mn0.06O2)。
Example 3
1. Weighing LiCoOOCH as lithium source in a certain metering molar ratio3Manganese source MnSO4Phosphorus source (NH)4)3PO4Adding carbon source carbon black into a certain amount of acetone solvent, wherein the ratio of Li: mn: p: the molar ratio of C is 0.99:1:1:0.225, and the solid-liquid ratio is 1: 40.
2. And (3) stirring and dispersing the mixture in the step (1) under a closed condition to form sol, wherein the dispersion rotating speed is set to be 1000r/min, and the stirring time is set to be 5.5 hr.
3. A certain amount of ternary cathode material LiNi is added0.83Co0.11Mn0.06O2Adding into the sol solution of step 2, stirring at 1000r/min for 2.5 hr.
4. And (3) stirring the mixed solution in the step (3) at a temperature of 90 ℃ while volatilizing the solvent, wherein the stirring speed is set to 250r/min, the stirring time is set to 3.5hr, the solvent is evaporated at a high temperature, and the sol is saturated and precipitated to form the microgel.
5. And (4) feeding the microgel mixed solution obtained in the step (4) into a spray dryer, setting the feeding temperature to be 250 ℃, the discharging temperature to be 90 ℃ and the rotational speed of an atomizer to be 20000rpm, so as to form a core-shell structure with the surface of the ternary cathode material being uniform in particle size and coated with gel, wherein the thickness of the coating layer is 50-100 nm.
6. And (3) coating the gel particles with the ternary cathode material formed in the step (5), putting the gel particles into a high-temperature reaction kettle, wherein the volume ratio of nitrogen to hydrogen is 5:5, heating to 250 ℃ at a heating rate of 3 ℃/min, and keeping the temperature for 5 hours; continuously heating to 500 deg.C at a speed of 2 deg.C/min for 3hr in the presence of nitrogen-hydrogen mixture at a volume ratio of nitrogen to hydrogen of 5: 5; continuously heating to 650 deg.C at 1 deg.C/min under hydrogen atmosphere, and maintaining for 8 hr.
7. And (3) introducing argon gas for protection into the particles in the step (6) in a high-temperature reaction kettle, cooling to 150 ℃ at the speed of 0.2 ℃/min, stopping introducing protective gas argon gas, cooling to room temperature at the speed of 3 ℃/min, cooling and screening to obtain the lithium ion battery composite anode material with the core-shell structure, wherein the shell structure of the anode material is polyanionic lithium salt with the chemical formula of LiMnPO4(ii) a The core structure of the anode material is composed of a ternary composite anode material, and the structural formula of the ternary composite anode material is LiNi0.83Co0.11Mn0.06O2)。
Example 4
1. Lithium source Li is weighed according to a certain metering molar ratio2CO3FeC as iron source2O4Phosphorus source (NH)4)H2PO4Adding a carbon source glucose into a certain amount of acetone solvent, wherein the ratio of Li: fe: p: the molar ratio of C is 0.99:1: 0.2, and the solid-to-liquid ratio is 1: 40.
2. And (3) stirring and dispersing the mixture in the step (1) under a closed condition to form sol, wherein the dispersion rotating speed is set to be 1000r/min, and the stirring time is set to be 5.5 hr.
3. Mixing a certain amount ofTernary positive electrode material LiNi0.83Co0.11Mn0.06O2Adding into the sol solution of step 2, stirring at 1000r/min for 2.5 hr.
4. And (3) stirring the mixed solution in the step (3) at a temperature of 90 ℃ while volatilizing the solvent, wherein the stirring speed is set to 250r/min, the stirring time is set to 3.5hr, the solvent is evaporated at a high temperature, and the sol is saturated and precipitated to form the microgel.
5. And (4) feeding the microgel mixed solution obtained in the step (4) into a spray dryer, setting the feeding temperature to be 250 ℃, the discharging temperature to be 90 ℃ and the rotational speed of an atomizer to be 20000rpm, so as to form a core-shell structure with the surface of the ternary cathode material with uniform particle size coated with gel, wherein the thickness of the coating layer is 50-100 nm.
6. Coating the ternary cathode material formed in the step (5) with gel particles, putting the gel particles into a high-temperature reaction kettle, and heating to 250 ℃ at a heating rate of 3 ℃/min under the condition of nitrogen for heat preservation for 5 hours; continuously heating to 500 deg.C at a rate of 2 deg.C/min under nitrogen condition, and maintaining for 3 hr; continuously heating to 650 deg.C at 1 deg.C/min under nitrogen atmosphere, and keeping the temperature for 8 hr.
7. And (3) introducing argon gas for protection into the particles in the step (6) in a high-temperature reaction kettle, cooling to 250 ℃ at the speed of 0.1 ℃/min, stopping introducing the protective gas of argon gas, cooling to room temperature at the speed of 2 ℃/min, cooling and screening to obtain the lithium ion battery composite anode material with the core-shell structure (the shell structure of the anode material is polyanionic lithium salt, and the chemical formula of the polyanionic lithium salt is LiFePO)4(ii) a The core structure of the anode material is composed of a ternary composite anode material, and the structural formula of the ternary composite anode material is LiNi0.83Co0.11Mn0.06O2)。
Comparative example 1
1. 1:50 of ternary positive electrode material LiNi0.83Co0.11Mn0.06O2Adding into reaction kettle with water, stirring at 1000r/min for 2.5 hr.
2. And (3) adjusting the pH value of the mixed solution obtained in the step (1) to be about 9, and adjusting the temperature in the reaction kettle to be 60 ℃.
3. And (3) adding a 2% aluminum acetate solution and the mixed solution in the step (1) into the mixed solution in the step (2) according to a mass ratio of 1:10, and simultaneously dropwise adding ammonia water to adjust the pH value to be 9.
4. And (4) filtering the mixed solution in the step (3), repeatedly washing filter residues by using deionized water, and drying.
5. And (4) placing the filter residue obtained in the step (4) in a high-temperature reaction kettle, heating to 500 ℃, and preserving heat for 3 hours.
6. And (5) cooling the high-temperature reaction kettle in the step (5) to room temperature, and screening to obtain the lithium ion composite ternary cathode material with the core-shell structure.
Preparing a lithium ion battery:
preparing a positive plate:
the positive electrode materials prepared in the above examples and comparative examples are used as positive electrode active materials, and the positive electrode active materials, the conductive agent carbon nanotubes, the conductive agent carbon black (Super Li), the adhesive polyvinylidene fluoride (PVDF), and the solvent N-methyl pyrrolidone are prepared into positive electrode slurry according to a certain proportion, wherein in the positive electrode slurry dry powder, the positive electrode active material proportion is as follows according to mass percentage: 96 percent, 0.5 percent of conductive agent carbon nano tube, 1.5 percent of conductive agent carbon black and 2 percent of binder; the prepared anode slurry is evenly coated on two sides of an aluminum foil, and the coating surface density is controlled to be 3.6g/100cm2And drying (at the condition of 125 ℃) to obtain a coil stock, rolling for 1 time, punching to obtain a positive plate, wherein the rolling compaction is controlled to be 3.4 g/cc.
Preparing a negative plate:
preparing anode slurry from artificial graphite (the trademark CP5M, the D50 is 16 mu m), a conductive agent carbon nano tube, styrene butadiene rubber serving as a binder, sodium carboxymethyl cellulose serving as a thickener and deionized water serving as a solvent according to a certain proportion, wherein in the anode slurry dry powder, the proportion of the anode active substances is as follows by mass percent: 95.5 percent of conductive agent, 1 percent of binder and 1.5 percent of thickening agent; the prepared negative electrode slurry is uniformly coated on two sides of a copper foil, and the coating surface density is controlled to be 2.0g/100cm2Drying (condition 70 deg.C)) And (4) obtaining a coil stock, rolling for 2 times, punching to obtain a negative plate, wherein the rolling compaction is controlled to be 1.5 g/cc.
Preparing an electric core: drying the obtained positive and negative plates, sequentially stacking the positive and negative plates and a diaphragm into a battery cell according to the sequence of diaphragm-negative plate-diaphragm-positive plate-diaphragm-negative plate, welding a positive aluminum tab and a negative copper nickel-plated tab on the battery cell by using an ultrasonic welding machine, and placing the welded battery cell into a well-punched aluminum plastic film for packaging, wherein the diaphragm is a PP-PE-PP film.
Battery core liquid injection: baking the packaged battery cell, injecting electrolyte, controlling the water content of the battery cell to be below 200ppm before injecting the electrolyte, sealing after injecting the electrolyte, and standing and activating the battery cell to enable the electrolyte to fully infiltrate the positive plate, the negative plate and the diaphragm. The baking conditions of the battery cell are as follows: the temperature is 82 ℃, the time is 25 hours, the electrolyte is a mixed solution of lithium salt, an additive and an organic solvent, the concentration of the lithium salt in the mixed solution is 1mol/L, the lithium salt is a mixture (8:2) of lithium hexafluorophosphate and lithium bis (fluorosulfonyl) imide, and the organic solvent is ethylene carbonate, diethyl carbonate and ethyl methyl carbonate (the volume ratio is 3:3: 4); the additive is vinylene carbonate, propyl sulfite, vinyl sulfate, lithium difluorophosphate and 1-propylene-1, 3-sultone, the volume percentage of the additive in the electrolyte is 3% (the weight ratio of the vinylene carbonate, the propyl sulfite, the vinyl sulfate, the lithium difluorophosphate and the 1-propylene-1, 3-sultone is 0.5%, 1%, 0.5%, 0.5% and 0.5%, respectively), and the battery cell is kept still under the following conditions: the temperature is 25 ℃ and the time is 45 h.
1. Cell formation: forming the activated battery cell under the conditions that the temperature is 25 ℃ and the pressure torque is 8 Nm, wherein the forming process comprises the following steps: the constant current is first charged to 3.6V with 0.05C, then to 3.8V with 0.1C, and finally to 3.9V with 0.2C, constant current and constant voltage, and the current is cut off at 0.01C.
2. And standing the formed battery cell for 45 hours at the temperature of 45 +/-2 ℃, then performing gas extraction, and performing 0.33C charging and discharging capacity grading on the battery cell after the gas extraction and edge sealing are finished.
TABLE 1
Figure BDA0002184967030000151
Figure BDA0002184967030000161
Residual lithium content testing: reference GB/T11064.1-2013
1. 30g of a sample to be tested was weighed in a 150mL beaker, and a magnetic stirrer and 100mL of pure water were added thereto, and the beaker was covered with a watch glass, and then placed on a magnetic stirrer, stirred for 30min, and then filtered.
2. 50mL of filtrate is measured by a graduated cylinder and placed in a conical flask, and 0.1-0.2mL of phenolphthalein indicator is added.
3. Titration with 0.05mol/L HCl standard titrant until the red color just disappeared was followed by the volume of HCl used V1.
4. Adding 0.1-0.2mL methyl red-bromocresol green indicator into the filtrate, continuously titrating with HCl until the filtrate turns from green to red, boiling for 2min to remove CO2, and cooling.
5. Titration was continued until the filtrate suddenly turned to wine red, which was the end point, and the HCl depleted volume V2 was recorded.
6. The residual amount of lithium hydroxide was: 0.05 × V1 × 23.94 × 2/50/30 × 1000000; the lithium carbonate residual amount is: 0.05 × V2-V1 × 36.94 × 2/50/30 × 1000000.
And (3) testing the cycle life: reference GB/T31484-
1. Under the environment of 25 +/-2 ℃, charging at a constant current of 1C to 4.2V and converting to constant voltage charging, and stopping when the current is reduced to 0.05C;
2. standing for 1h at the temperature of 25 +/-2 ℃;
3. discharging to 2.75V at constant current of 1C under the environment of 25 +/-2 ℃;
4. standing for 1h at the temperature of 25 +/-2 ℃;
5. repeating the steps 1-4 until the discharge capacity is lower than 80% of the initial discharge capacity, and terminating.
And (3) testing the high-temperature storage performance: reference GB/T31486-
1. Under the environment of 25 +/-2 ℃, charging at a constant current of 1C to 4.2V for constant voltage charging, stopping when the current is reduced to 0.05C, standing for 1h, reducing to 2.75V at a constant current of 1C, and recording the initial discharge capacity as Q1;
2. under the environment of 25 +/-2 ℃, charging at a constant current of 1C to 4.2V and converting to constant voltage charging, and stopping when the current is reduced to 0.05C;
3. standing at 55 +/-2 ℃ for 28 days, taking out, and standing at room temperature for 12 hours;
4. reducing the voltage to 2.75V at a constant current of 1C under the environment of 25 +/-2 ℃, and recording the discharge capacity as Q2;
5. under the environment of 25 +/-2 ℃, charging at a constant current of 1C to 4.2V and converting to constant voltage, stopping when the current is reduced to 0.05C, standing for 1h, reducing to 2.75V at a constant current of 1C, and recording the discharge capacity as Q3;
6. the charge retention rate is Q2/Q1, and the capacity recovery rate is Q3/Q1.
The results in table 1 show that the residual lithium content of the composite ternary cathode material with the core-shell structure is obviously reduced compared with that of the ternary cathode material without the core-shell structure, and the cycle life and the storage performance of the prepared battery are obviously improved. Meanwhile, when the composite ternary cathode material of examples 1, 2 and 3 in which polyanionic lithium salt is used as the shell structure according to the present invention is used, the content of residual lithium is further reduced compared to comparative example 1 in which metal oxide is used as the shell structure, which shows that residual lithium can be consumed as a reactant in the process of forming the shell. The lithium ion batteries prepared from the composite ternary cathode materials in examples 1, 2 and 3 have better cycle life and storage performance.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (10)

1. The lithium ion battery anode material with the core-shell structure is characterized in that the shell structure of the anode material is polyanionic lithium salt with the chemical formula of LiβRAO4(ii) a The core structure of the anode material is composed of a ternary complexA composite anode material with a structural formula of LiαNixCoyM1-y-xO2Wherein R is selected from Mn and/or Fe, A is P and/or Si, and M is Mn and/or Al.
2. The positive electrode material according to claim 1, wherein β is in a range of 0.8 to 2, α is in a range of 0.5 to 1.2, x and y are in a range of 0 to 1, and x + y is less than 1.
3. A method for producing the positive electrode material according to claim 1 or 2, characterized by comprising:
(1) weighing a lithium source, an R compound source, an A compound source and a carbon source according to a metered molar ratio, and adding the lithium source, the R compound source, the A compound source and the carbon source into a solvent;
(2) stirring and dispersing the mixture in the step (1) under a closed condition to form sol;
(3) at normal temperature, the ternary cathode material LiαNixCoyM1-y-xO2Adding the mixture into the sol obtained in the step (2), and stirring and mixing to obtain a mixed solution;
(4) heating the mixed solution in the step (3) to a temperature lower than 100 ℃, stirring, and carrying out saturated precipitation to form microgel;
(5) sending the microgel obtained in the step (4) into a spray dryer for spray drying to form a core-shell structure with uniform particle size and a gel-coated surface of the ternary cathode material, wherein the thickness of the coating layer is 50-100 nm;
(6) and (3) under a reducing atmosphere, at the temperature of 500-800 ℃, putting the gel core-shell structure material coated by the ternary cathode material formed in the step (5) into a high-temperature reaction kettle for reaction, and then cooling and screening.
4. The method of claim 3, wherein,
in the step (1), the molar ratio of Li and C of the lithium source to the carbon source is 4-5: 1;
in the step (2), the stirring speed is set to be 500-; preferably, the stirring speed is set to 900-1100r/min, and the stirring time is 5-6 hr;
in the step (3), the stirring speed is set to be 500-; preferably, the stirring speed is set to 900-1100r/min, and the stirring time is 2-3 hr;
in the step (4), the stirring speed is set to 200-300r/min, and the stirring time is set to 1-12 hr; preferably at 60-100 deg.C, preferably 80-95 deg.C, and stirring for 2.5-4.5 hr;
in the step (5), the spray drying conditions comprise that the feeding temperature is 150-;
in the step (6), the reduction conditions include: the temperature is 600-650 deg.C, and the time is 2-12hr, preferably 6-8 hr;
the reducing gas is one or more of carbon monoxide, hydrogen and a nitrogen-hydrogen mixed gas.
5. The method of claim 3 or 4, wherein in step (6), the step of reducing comprises: under the condition of nitrogen-hydrogen mixed gas, preferably selecting the volume ratio of nitrogen to hydrogen (3:7) - (6:4), heating to 200-300 ℃ at the heating rate of 1-5 ℃/min, and carrying out heat preservation for 4-6 h; continuously heating to 400-500 ℃ at the heating rate of 1-5 ℃/min and keeping the temperature for 2-4hr in the presence of nitrogen-hydrogen mixed gas, preferably in the volume ratio of nitrogen to hydrogen (3:7) - (6: 4); finally, under the hydrogen atmosphere, the temperature is raised to 800 ℃ at the temperature raising rate of 1-5 ℃/min, preferably 650 ℃ at the temperature of 600-.
6. The method of claim 3 or 4, wherein the conditions of cooling comprise: introducing argon gas for protection, cooling to 150 ℃ and 250 ℃ at the speed of 0.1-0.5 ℃/min, stopping introducing protective gas argon gas, and cooling to room temperature at the speed of 2-5 ℃/min.
7. The method of claim 3 or 4,
the lithium source is one or more of lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate and lithium citrate;
the R compound source is an iron source and/or a manganese source, the iron source is one or more of ferrous oxalate, ferrous acetate, ferric phosphate and ferric oxide, and the manganese source is one or more of manganese sulfate, manganese dioxide and manganese carbonate;
the compound A source is a phosphorus source and/or a silicon source, the phosphorus source is one or more of ammonium dihydrogen phosphate, ammonium hydrogen phosphate and ammonium phosphate, and the silicon source is tetraethoxysilane and/or methyl orthosilicate;
the carbon source is one or more of glucose, sucrose and carbon black;
the solvent is one or more of acetone, diethyl ether and absolute ethyl alcohol;
the ternary positive electrode material is LiNi0.8Co0.1Mn0.1O2、LiNi0.83Co0.11Mn0.06O2、LiNi0.8Co0.1Al0.1O2、LiNi0.6Co0.2Mn0.2O2And LiNi0.5Co0.3Mn0.2O2One or more of (a).
8. A positive electrode sheet, comprising a positive electrode current collector and a positive electrode active material layer coated on the positive electrode current collector, wherein the positive electrode active material of the positive electrode active material layer is partially or completely derived from the positive electrode material of claim 1 or 2 or the positive electrode material prepared by the preparation method of any one of claims 3 to 7.
9. A lithium ion battery, the lithium ion battery comprising: the lithium ion battery comprises a positive plate, a negative plate, a diaphragm, electrolyte, a positive tab, a negative tab and an aluminum plastic film, and is characterized in that the positive plate is the positive plate in claim 8.
10. The use of the lithium ion battery of claim 9 in a new energy vehicle.
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