CN107665983B - Lithium ion battery positive electrode material, preparation method thereof and lithium ion battery - Google Patents

Lithium ion battery positive electrode material, preparation method thereof and lithium ion battery Download PDF

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CN107665983B
CN107665983B CN201710667570.XA CN201710667570A CN107665983B CN 107665983 B CN107665983 B CN 107665983B CN 201710667570 A CN201710667570 A CN 201710667570A CN 107665983 B CN107665983 B CN 107665983B
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lithium
ion battery
nickel cobalt
precursor
lithium ion
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CN107665983A (en
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孔令涌
尚伟丽
陈俊奇
李洁凤
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Shenzhen Dynanonic Co ltd
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Shenzhen Dynanonic Co ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/37—Phosphates of heavy metals
    • C01B25/375—Phosphates of heavy metals of iron
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • 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
    • H01M4/36—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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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 provides a lithium ion battery anode material which is characterized by comprising nickel cobalt lithium manganate and a coating layer arranged on the surface of the nickel cobalt lithium manganate, wherein the coating layer is made of lithium vanadium iron phosphate or lithium vanadium oxygen phosphate. The cladding material is close to the voltage platform of the nickel cobalt manganese acid lithium, so that the safety and the cycle performance of the nickel cobalt manganese ternary material can be well improved, and higher energy density can be kept. The invention also provides a preparation method of the lithium ion battery anode material and a lithium ion battery.

Description

Lithium ion battery positive electrode material, preparation method thereof and lithium ion battery
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a lithium ion battery anode active material, a preparation method thereof and a lithium ion battery.
Background
Lithium ion batteries are a new generation of green high-energy batteries, and increasingly play an important role in various fields. As an important component of lithium ion batteries, the positive electrode material of lithium batteries determines the performance, price and development of lithium batteries. The nickel-cobalt-manganese ternary cathode material is a novel lithium ion battery cathode material, has the advantages of high energy density, high voltage platform, ideal crystal structure, small self-discharge, no memory effect and the like, but has poor thermal stability and safety, and the cycle performance under high charge cut-off voltage is not ideal.
In order to solve the problems of safety and cycle performance of the nickel-cobalt-manganese ternary cathode material, in the prior art, materials such as lithium iron phosphate are generally adopted to coat and modify the nickel-cobalt-manganese ternary cathode material so as to reduce the influence of the de-intercalation of lithium ions on the crystal structure of the nickel-cobalt-manganese lithium material in the charging and discharging processes, but the electronic conductivity of the lithium iron phosphate is poor, the voltage platform is much lower than that of the nickel-cobalt-manganese ternary material, and the cycle performance and the safety performance of the modified cathode material are not well improved.
Disclosure of Invention
In order to solve the problems, the invention provides a lithium ion battery anode material, and the lithium ion battery anode active material adopts a material (lithium vanadium iron phosphate or lithium vanadium oxygen phosphate) close to a voltage platform of a nickel-cobalt-manganese ternary material as a coating layer to modify the surface of the nickel-cobalt-manganese ternary material, so that the safety and the cycle performance of the nickel-cobalt-manganese ternary material can be well improved, and higher energy density can be kept. The invention also provides a preparation method of the lithium ion battery anode material, which is unique and effective and can uniformly coat the surface of the nickel-cobalt-manganese ternary material with the coating material.
Specifically, the first aspect of the invention provides a lithium ion battery cathode material, which comprises nickel cobalt lithium manganate and a coating layer arranged on the surface of the nickel cobalt lithium manganate, wherein the coating layer is made of lithium vanadium iron phosphate or lithium vanadium oxygen phosphate.
Wherein the voltage platform of the nickel cobalt lithium manganate is 3.6-3.8V. In the application, the voltage platform means that when the battery is charged and discharged at constant current, the voltage of the battery has a stable process (almost no change or very small change), and the stable value is the charging and discharging platform; this plateau takes up a significant portion of the total charge or discharge time.
Wherein the voltage platform of the lithium vanadium iron phosphate is 3.6-3.7V; the voltage platform of the lithium vanadyl phosphate is 3.8-3.9V.
The charging and discharging range of the common nickel cobalt lithium manganate ternary positive electrode material is 4.3-2.7V, the lithium vanadium iron phosphate is 4.3-2.6V, and the lithium vanadyl phosphate is 4.2-2.8V, in the invention, a material (lithium vanadium iron phosphate or lithium vanadyl phosphate) close to the voltage platform of the nickel cobalt lithium manganate ternary material is adopted as a coating layer, so that the problems that when the material (such as lithium iron phosphate, the charging and discharging range is 3.8-2.0V) with the voltage platform far lower than that of the nickel cobalt lithium manganate is adopted for coating, the coating layer is overcharged at an overhigh charging voltage, and the matrix nickel manganese ternary material is overdischarged at an overlow lithium iron discharging voltage can be avoided, the safety and the cycle performance of the obtained lithium ion battery positive electrode material are further improved, and higher energy density can be kept.
Wherein the thickness of the cladding layer is 200-700 nm. For example, it may be 300, 400, 450, 500 or 600 nm.
Wherein the mass ratio of the material of the coating layer to the nickel cobalt lithium manganate is (5-15): (85-95), i.e. 1: (5.7-19). Preferably 1: (8-19). More preferably 1: (15-19). The coating layer material and the nickel cobalt lithium manganate with the appropriate mass ratio can ensure that a coated positive electrode material with a stable structure is formed, the positive electrode material has better stability and better electrochemical performance, and in addition, the capacity of the positive electrode material can be adjusted by adjusting the mass ratio.
Wherein the coating material is discontinuously (i.e. discontinuously) attached to the surface of the nickel cobalt lithium manganate. Further, the area covered by the coating layer accounts for 85-95% of the total surface area of the nickel cobalt lithium manganate.
Wherein the nickel cobalt lithium manganate is spherical and has a chemical formula of LiNixCoyMn1-x-yO2X and y represent mole percent, 0<x，y<1. Preferably, x ranges from 0.4 to 0.6.
Furthermore, the particle size of the nickel cobalt lithium manganate is 9-15 μm.
Wherein the chemical formula of the lithium vanadium iron phosphate is LiFeaVbPO4(abbreviated as LFVP), a and b represent molPercent, 0 < a < 1, 0 < b < 2/3, and 2a +3b 2; the valence of Fe is +2, and the valence of V is + 3.
When the material of the coating layer is lithium vanadium iron phosphate, the particle size of the lithium ion battery anode material is micron-sized, and is preferably 10-30 μm. The compacted density of the lithium ion battery anode material is 3.5-3.7g/cm3. The capacity and the compaction density of the lithium ion battery anode active material are higher, so that the energy density of the battery is more favorably improved, and the application field of the battery prepared by the material is expanded.
When the coating material is lithium vanadyl phosphate (LiVOPO4), the particle size of the lithium ion battery anode material is micron-sized, and preferably 1-1000 μm. The compacted density of the lithium ion battery anode material is 3.5-3.7g/cm3。
In the lithium ion battery anode material provided by the first aspect of the invention, because the lithium iron vanadium phosphate or lithium vanadyl phosphate close to the voltage platform of the nickel-cobalt-manganese ternary material is adopted as the coating layer of the nickel-cobalt-manganese ternary material, compared with the lithium iron phosphate material with a lower voltage platform, the problems of overcharge caused to the coating layer and overdischarge caused to the coated ternary material when the voltage range of the coating layer material and the ternary material is not matched can be avoided, and the obtained anode material has good stability, high safety, good cycle performance and higher energy density.
The invention provides a preparation method of a lithium ion battery anode material, which comprises the following steps:
providing a coating layer material, wherein the coating layer material is lithium vanadium iron phosphate or lithium vanadyl phosphate;
adding a first solvent and a film-forming agent into the coating material, uniformly mixing to obtain a dispersion liquid of the coating material, adding nickel cobalt lithium manganate, mixing for 0.5-4h, drying the obtained mixture at 90-160 ℃ in vacuum, and sieving the dried solid with a screen of 300 meshes and 400 meshes to obtain a lithium ion battery anode material, wherein the lithium ion battery anode material comprises nickel cobalt lithium manganate and a coating layer arranged on the surface of the nickel cobalt lithium manganate; the film forming agent comprises at least one of polyvinyl alcohol, polyethylene glycol, povidone, sodium dodecyl benzene sulfonate and stearic acid.
Wherein the mass ratio of the coating layer material to the nickel cobalt lithium manganate is (5-15): (85-95), i.e. 1: (5.7-19). Preferably 1: (8-19). More preferably 1: (15-19).
In this application, the film-forming agent has certain viscosity, still possesses the surfactant action, helps nickel cobalt manganese ternary material to adsorb the cladding material, and nickel cobalt manganese ternary material can make the cladding material cladding on nickel cobalt manganese ternary material surface evenly through mixing the stirring in the dispersion of cladding material.
Preferably, when the coating material is lithium vanadyl phosphate, the dispersion liquid of the coating material further contains a conductive adhesive, and the conductive adhesive is one or more of super p (carbon black), ketjen black, acetylene black, and carbon nanofibers (such as Vapor-grown carbon fibers (VGCF)). The conductive adhesive can improve the conductivity of lithium vanadyl phosphate.
Preferably, when the dispersion liquid of the coating layer material is mixed with the nickel cobalt lithium manganate, the stirring speed is 200-500 rpm.
Wherein the first solvent comprises at least one of N-methylpyrrolidone, dimethyl sulfoxide, acetone, water and ethanol. The first solvent can be selected according to the selected film forming agent, so that the film forming agent is fully dissolved as much as possible.
Preferably, before the vacuum drying of the mixture, the method further comprises: centrifuging the obtained mixture at 1000-3000 rpm for 20-60 minutes, removing supernatant, and collecting precipitate. The subsequent vacuum drying was performed on the pellet obtained after centrifugation.
The preparation process of the coating material comprises the following steps: providing a coating material precursor, presintering the coating material precursor at the constant temperature of 200-400 ℃ for 2-4h under protective gas, then carrying out ball milling on the presintered coating material precursor, and sintering the ball-milled coating material precursor; wherein, the sintering process comprises the following steps: the temperature is raised to 250 ℃ for 150-.
When the precursor of the cladding material is a lithium iron vanadium phosphate precursor, sintering is carried out under a protective gas; when the precursor of the cladding layer material is a lithium vanadyl phosphate precursor, the sintering is carried out in the air or under the mixed atmosphere of oxygen and protective gas.
Further, in the sintering process, the heating rate of heating to 150-250 ℃ is 1-5 ℃/min; the heating rate from the temperature of the first constant temperature sintering (i.e. 150 ℃ C. -250 ℃ C.) to the temperature of the second constant temperature sintering (550 ℃ C. -700 ℃ C.) is 1-3 ℃/min.
According to the invention, the coating material precursor is pre-sintered under protective gas, impurities (such as excessive complexing agent, reducing agent and the like) in the coating material precursor can be removed through the pre-sintering, and the formation of a crystal lattice part in the coating material precursor is facilitated, so that a semi-finished product is formed; then, ball-milling the presintered coating material precursor, and then performing sectional sintering, wherein the sintering temperature is not too high, and the sintering time is not too long, so that the coating material precursor can be fully sintered, and in addition, the sectional sintering is more beneficial to improving the lattice goodness of the coating material; the ball milling of the sectional sintering is beneficial to refining the precursor particles of the cladding layer material, homogenizing the components, increasing the activity to better nucleate and grow up, and avoiding the poor nucleation of the crystal grains of the cladding layer material and the low yield.
Wherein the protective gas is at least one of nitrogen, argon and helium. The pre-firing is performed in a protective gas. The pre-sintering in the protective gas can prevent the ferrous ions in the lithium vanadium iron phosphate from being oxidized.
Wherein, the particle size of the coating material precursor obtained after ball milling is 100-300 nm.
In the invention, the preparation method of the coating material precursor can be the conventional method, such as a high-temperature solid phase reduction method, a sol-gel method, a spray drying method, a hydrothermal method or a microwave method.
In an embodiment of the present invention, when the material of the coating layer is lithium vanadium iron phosphate, a preparation process of the lithium vanadium iron phosphate precursor is as follows: lithium source, vanadium source, iron source and phosphorus source are mixed according to the mol ratio of Li: fe: v: p is 1: a: b: 1, weighing, adding a second solvent, a complexing agent and/or a reducing agent, mixing and dispersing to obtain a mixed slurry, adjusting the pH of the mixed slurry to be 1-7, and performing vacuum drying on the obtained mixed slurry at 90-160 ℃ to obtain a lithium vanadium iron phosphate (LFVP) precursor; wherein 0 < a < 1, 0 < b < 2/3, and 2a +3b 2.
Preferably, the mixed slurry is formed as follows: adding a solvent, a complexing agent and/or a reducing agent into the vanadium source for dissolving to obtain a vanadium source solution; and mixing the lithium source, the iron source, the phosphorus source and a solvent, and adding a dissolved vanadium source solution to obtain the mixed slurry.
Wherein the lithium source is selected from at least one of lithium hydroxide, lithium chloride, lithium nitrate, lithium oxalate, lithium acetate, lithium carbonate, etc., lithium phosphate, lithium dihydrogen phosphate, and lithium dihydrogen phosphate; the vanadium source is selected from vanadium pentoxide (V)2O5) Ammonium metavanadate (NH)4VO3) At least one of; the iron source is at least one selected from ferrous nitrate, ferrous oxalate and ferrous chloride; the phosphorus source is at least one selected from ammonium dihydrogen phosphate, ammonium monohydrogen phosphate, ammonium phosphate and phosphoric acid; the complexing agent is at least one selected from citric acid, ascorbic acid, oxalic acid, tartaric acid, EDTA (ethylene diamine tetraacetic acid), potassium complex and thiourea; the second solvent is at least one selected from water, ethanol, ethylene glycol, propanol, isopropanol, isobutanol, methanol and n-butanol.
In another embodiment of the present invention, when the coating material is lithium vanadyl phosphate, the preparation process of the lithium vanadyl phosphate precursor is as follows: and (2) mixing a lithium source, a vanadium source and a phosphorus source according to the mol ratio of Li: fe: v: p is 1: a: b: 1, adding a second solvent, a complexing agent and/or a reducing agent, stirring in a water bath at 65-100 ℃ to obtain mixed slurry, and performing vacuum drying on the mixed slurry at 90-160 ℃ to obtain the lithium vanadyl phosphate precursor.
Wherein the complexing agent is at least one selected from citric acid, ascorbic acid, oxalic acid, tartaric acid, EDTA, potassium complex and thiourea; the reducing agent is at least one selected from citric acid, oxalic acid, sucrose, glucose, sodium sulfite and sodium thiosulfate. Further, the complexing agent and the reducing agent may be the same substance, for example both citric acid or oxalic acid.
According to the preparation method of the lithium ion battery anode material provided by the second aspect of the invention, the coating material, the film forming agent and the solvent are mixed with the nickel cobalt lithium manganate, and the nickel cobalt lithium manganate coated with the coating is obtained after vacuum drying.
The third aspect of the invention provides a preparation method of a lithium ion battery anode material, which comprises the following steps:
providing a coating material precursor, wherein the coating material precursor is a lithium iron vanadium phosphate precursor or a lithium vanadyl phosphate precursor; pre-burning the coating material precursor at the constant temperature of 200-400 ℃ for 2-4h in protective gas, and cooling to obtain the pre-burned coating material precursor;
dissolving the presintered coating material precursor in a water-soluble polar solvent, adding nickel cobalt lithium manganate into the water-soluble polar solvent, mixing for 0.5 to 10 hours to obtain first slurry, and drying the first slurry at 90 to 160 ℃ in vacuum to obtain a positive electrode material precursor;
sintering the precursor of the positive electrode material, wherein the sintering process comprises the following specific steps: firstly heating to 250 ℃ for 150-; and after cooling, sieving the solid obtained by sintering by a 400-mesh sieve of 300 meshes to obtain the lithium ion battery anode material, wherein the lithium ion battery anode material comprises nickel cobalt lithium manganate and a coating layer arranged on the surface of the nickel cobalt lithium manganate.
When the precursor of the positive electrode material contains a lithium vanadium iron phosphate precursor, sintering is carried out under a protective gas; when the precursor of the positive electrode material contains the lithium vanadyl phosphate, the sintering is carried out in the air or in the mixed atmosphere of oxygen and protective gas.
Wherein the mass ratio of the presintered coating material precursor to the nickel cobalt lithium manganate is (5-15): (85-95), i.e. 1: (5.7-19).
Wherein the water-soluble polar solvent is selected from one or more of water, ethanol, ethylene glycol, N-methyl pyrrolidone, dimethyl sulfoxide and acetone.
Wherein the protective gas is at least one of nitrogen, argon and helium.
The method for mixing the presintered coating material precursor and the nickel cobalt lithium manganate can be stirring, ultrasonic processing, ball milling, sand milling or high-speed dispersion, and only needs to mix the materials uniformly, and the specific mode is not particularly limited.
According to the invention, a coating material precursor is pre-sintered under a protective atmosphere, and the pre-sintering can help to form a crystal lattice part in the coating material precursor, so that a semi-finished product is formed; then, mixing the presintered coating material precursor with lithium nickel cobalt oxide, and continuing to perform segmented sintering, so that the coating material precursor and the lithium nickel cobalt oxide can be fully sintered at the sintering temperature without being too high and the sintering time without being too long, and a uniform coating layer can be fully formed on the surface of the lithium nickel cobalt oxide; in addition, the segmented sintering is more beneficial to improving the lattice perfection of the cladding material.
According to the preparation method of the lithium ion battery anode material provided by the third aspect of the invention, the pre-sintered coating layer material precursor and the lithium nickel cobalt oxide are mixed and coated firstly, and then the obtained anode material precursor is sintered to obtain the coating layer coated lithium nickel cobalt manganese oxide anode material.
The whole sintering process of the invention is carried out in a constant temperature furnace, and any heat treatment equipment which can uniformly heat under the protection of atmosphere can be used in the sintering process, such as a vacuum furnace, a box furnace, a tunnel furnace, a rotary atmosphere furnace, a bell jar furnace, a tubular furnace, a shuttle furnace or a pushed slab kiln.
In a fourth aspect of the invention, a lithium ion battery is provided, which comprises the lithium ion battery anode material provided by the first aspect of the invention.
The lithium ion battery comprises a positive pole piece, a negative pole piece, a diaphragm, electrolyte and a shell, wherein the positive pole piece consists of a current collector, the lithium ion battery positive material provided by the first aspect of the invention, a conductive agent and an adhesive.
In the embodiment of the invention, the current collector is an aluminum foil, a nickel mesh or an aluminum-plastic composite film.
In an embodiment of the present invention, the conductive agent is acetylene black.
In the embodiment of the invention, the binder is polyvinylidene fluoride (PVDF), styrene butadiene rubber latex (SBR) or sodium carboxymethylcellulose (CMC).
The selection of the negative electrode plate, the separator, the electrolyte and the housing is the prior art in the industry, and is not limited herein.
The lithium ion battery provided by the fourth aspect of the invention has higher energy density, cycle performance and safety.
Advantages of embodiments of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of embodiments of the invention.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of a lithium iron vanadium phosphate precursor after pre-firing in example 1 of the invention;
FIG. 2 is an SEM photograph of a lithium vanadium iron phosphate finished product prepared in example 1 of the present invention;
FIG. 3 is an SEM photograph of lithium nickel cobalt manganese oxide used in example 1 of the present invention;
FIG. 4 is an SEM photograph of the positive electrode material of the lithium ion battery prepared in example 1 of the present invention;
FIG. 5 is an XRD (X-ray diffraction) pattern of the lithium ion battery positive electrode material prepared in example 1 of the present invention;
fig. 6 is a DSC curve of button cells made using the positive electrode materials of examples 1-3 of the present invention and comparative examples 1-3.
Detailed Description
While the following is a description of the preferred embodiments of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Example 1:
a preparation method of a lithium ion battery anode material comprises the following steps:
(1) preparation of lithium vanadium iron phosphate precursor
Weighing 0.55g of vanadium pentoxide and 9g of oxalic acid, adding 12mL of deionized water, heating to 60 ℃, and fully stirring to dissolve the raw materials to obtain a vanadium source solution; weighing 7.46g of lithium carbonate, 79.17g of ferric nitrate and 23.24g of ammonium dihydrogen phosphate, dissolving in 45mL of nitric acid, adding a dissolved vanadium source solution, and stirring for 1h to obtain a mixed slurry; and (3) drying the obtained mixed slurry at 150 ℃ in vacuum to obtain a lithium vanadium iron phosphate (LFVP) precursor.
(2) Pre-sintering of LFVP precursor: and (3) heating the dried LFVP precursor powder to 300 ℃ at the speed of 5 ℃/min under the protection of nitrogen atmosphere, and preserving the temperature for 2h to obtain the pre-sintered LFVP precursor powder.
(3) Preparing an LFVP finished product: adding agate beads into the pre-sintered LFVP precursor according to the ball-powder ratio of 10:1, and performing ball milling refinement on the precursor powder by using an agate grinding tank for 300rpm/2h, wherein the particle size of the ball-milled LFVP precursor is about 200 nm.
And (3) sintering the thinned LFVP precursor powder in a segmented manner under the protection of nitrogen, heating to 200 ℃ at the speed of 2 ℃/min, sintering at a constant temperature for 2h, heating to 700 ℃ at the speed of 2 ℃/min, sintering at a constant temperature for 8h, and cooling along with the furnace to obtain a finished product of lithium vanadium iron phosphate (LFVP).
(4) Preparing a ternary raw material/lithium vanadium iron phosphate composite cathode material:
adding 6.4g of the obtained lithium vanadium iron phosphate into 100g N-methyl pyrrolidone, adding 1.5g of polyvinyl alcohol, stirring and dissolving for 0.5h to obtain a dispersion liquid of a coating material;
100g of a Ni-Co-Mn ternary material Li (Ni) was weighed0.5Co0.2Mn0.3)O2(the average particle size is 14.5 microns), adding the mixture into the dispersion liquid of the coating material, continuously stirring for 1.5h, centrifuging at 1000rpm for 0.5h, removing the supernatant, collecting the precipitate, and drying the obtained precipitate at 120 ℃ in vacuum for 1h to obtain the cathode material with a coating structure, namely the lithium nickel cobalt manganese oxide coated by the lithium vanadium iron phosphate.
Preparation method of lithium ion battery
Adding 800g of the lithium ion battery anode material prepared by the method, 100g of conductive agent acetylene black and 100g of binder polyvinylidene fluoride (PVDF) into 800g of N-methylpyrrolidone solution (NMP solution), and stirring for 2h in a vacuum stirrer to prepare anode slurry; the slurry was uniformly coated on an aluminum foil, then dried in a vacuum oven at 120 ℃ for 12 hours, and then punched into a disk with a diameter of 14mm as a positive electrode. A positive plate, a negative plate (a metal lithium plate with the diameter of 14.5 mm), a diaphragm (Celgard 2400 microporous polypropylene film) and an electrolyte (1mo1/L LiPF)6the/EC + DMC (1: 1 by volume)) was assembled into a CR2025 button cell in a hydrogen-filled glove box, and the cell was left to stand for 12h before performing electrochemical performance tests. When electrochemical performance test is carried out, the constant temperature of 25 ℃ is kept, metal Li is used as a counter electrode, the charging and discharging voltage range is 2.7-4.3V, and the constant temperature of 25 ℃ is kept.
The following 3 test items of the battery were tested:
(a) first 0.2C specific discharge capacity (mAh/g): charging and discharging at a current density of 0.2C under a charging and discharging voltage of 4.3-2.7V;
(b) capacity retention (%) after 100 cycles at 1C: circulating the current density at 1C for 100 times under the condition that the charging and discharging voltage is 4.3-2.7V;
(c) the 1C median voltage is 4.3-2.7V, and the first 1C median voltage during discharge;
fig. 1 and fig. 2 are Scanning Electron Microscope (SEM) photographs of a lithium iron vanadium phosphate (LFVP) precursor and an LFVP product after pre-firing in example 1, respectively, and fig. 3 is an SEM photograph of nickel cobalt lithium manganate used in example 1; fig. 4 is an SEM photograph of the lithium ion battery positive electrode material obtained in example 1;
as can be seen from fig. 1, the LFVP precursor has a relatively regular morphology and a partial lattice is formed by pre-firing; the LFVP finished product after sintering is granular, and the average grain diameter is 500-600 nm; when the LFVP finished product is used for coating the near-spherical nickel cobalt lithium manganate with the particle size of 10-15 μm, a positive electrode material (shown in figure 4) with a smooth surface, a regular shape and a compact and stable structure can be formed, and the particle size is about 15 μm. Through calculation, in the obtained cathode material, the mass ratio of the lithium iron vanadium phosphate to the lithium nickel cobalt manganese oxide is 1: 16, the thickness of the coating layer (lithium iron vanadium phosphate) is 510 nm.
The positive electrode material was subjected to XRD measurement at the same time, and the measurement result is shown in fig. 5. As can be seen from fig. 5, the positive electrode active material of the lithium ion battery prepared in example 1 of the present invention has a strong and sharp X-ray diffraction peak intensity, which indicates that the prepared positive electrode material of the lithium ion battery has good crystallinity, and tests on a standard PDF card show that the positive electrode material of the lithium ion battery has characteristic patterns of LFVP and nickel cobalt lithium manganate at the same time, which indicates that the positive electrode active material of the lithium ion battery prepared in the present invention is formed by compounding LFVP and nickel cobalt lithium manganate.
The lithium ion battery prepared in the embodiment 1 of the invention is subjected to charge and discharge tests within the voltage range of 4.3-2.7V, and the first discharge gram capacity of the lithium ion battery under the multiplying power of 0.2C is measured to be about 173.6 mAh/g; and calculating the first charge-discharge efficiency, wherein the first charge-discharge efficiency is the first discharge capacity/the first charge capacity. The first charge-discharge efficiency of the battery is calculated to reach 90.2%. The positive electrode active material of the battery provided by the invention has the advantages of high gram capacity, stable discharge platform and excellent performance.
The lithium ion battery prepared in example 1 was subjected to cycle performance testing, the charge-discharge voltage was 4.3-2.7V, and the capacity retention ratio was 98.5% after 100 cycles at 1.0C, indicating that the cycle performance was good. The median voltage of the lithium ion battery prepared in example 1 was measured to be 3.74V at 1.0C.
Example 2:
a preparation method of a positive active material of a lithium ion battery comprises the following steps:
(1) preparation of lithium vanadium iron phosphate precursor
Weighing 0.092g of vanadium pentoxide, adding 5mL of hydrogen peroxide, and stirring to dissolve completely to obtain a vanadium source solution; weighing 7.46g of lithium carbonate, 81.2g of ferric nitrate and 23.24g of ammonium dihydrogen phosphate, dissolving in 30mL of nitric acid, adding a dissolved vanadium source solution, weighing 2.11g of citric acid as a complexing agent, complexing the substances, stirring for 2 hours, and carrying out vacuum drying on the obtained mixed slurry at 150 ℃ to obtain a lithium vanadium phosphate (LFVP) precursor.
(2) Pre-sintering of LFVP precursor: and (3) heating the dried LFVP precursor powder to 250 ℃ at the speed of 5 ℃/min under the protection of nitrogen atmosphere, and preserving heat for 3h to obtain the pre-sintered LFVP precursor powder.
(3) Mixing the ternary raw material/lithium vanadium iron phosphate precursor: adding 5.6g of the LFVP precursor powder subjected to pre-sintering into 60g of alcohol, stirring and dissolving for 0.5h to obtain a dispersion liquid of the LFVP precursor;
100g of a Ni-Co-Mn ternary material Li (Ni) was weighed0.5Co0.2Mn0.3)O2(average particle size 12.4 μm), adding into the alcohol dispersion of LFVP precursor, stirring for 1.5h, and vacuum drying the obtained slurry at 100 deg.C for 1h to obtain mixed powder;
(4) preparing a ternary raw material/lithium vanadium iron phosphate composite cathode material: and sintering the dried mixed powder in a nitrogen atmosphere in a segmented manner, heating to 150 ℃ at the speed of 2 ℃/min, sintering at a constant temperature for 2h, heating to 600 ℃ at the speed of 2 ℃/min, sintering at a constant temperature for 10h, and cooling along with a furnace to obtain the composite cathode material with a coating structure.
The preparation method of the lithium ion battery is the same as that of example 1.
Through calculation, in the obtained cathode material, the mass ratio of the lithium iron vanadium phosphate to the lithium nickel cobalt manganese oxide is 1: 18.5, the thickness of the coating layer (lithium iron vanadium phosphate) is 430 nm.
Example 3:
a preparation method of a positive active material of a lithium ion battery comprises the following steps:
(1) preparation of lithium vanadium oxy phosphate precursor
Weighing ammonium metavanadate 4.68g, ammonium dihydrogen phosphate 4.60g and oxalic acid 20.82g, and dissolving in waterStirring for 2 hours in 350mL of deionized water in a water bath kettle at 70 ℃ to fully dissolve; then adding 0.99g of lithium hydroxide and 1.0g of cane sugar, and continuously stirring for reaction for 10 hours to obtain mixed slurry; vacuum drying the obtained mixed slurry at 100 ℃ for 4h to obtain lithium vanadium oxide phosphate (LiOVPO)4) And (3) precursor.
(2)LiOVPO4Pre-sintering of a precursor: drying LiOVPO4Heating the precursor powder to 300 ℃ at the speed of 4 ℃/min under the protection of nitrogen atmosphere, and preserving heat for 2h to obtain the pre-sintered LiOVPO4And (3) precursor powder.
(3) Preparing a finished product of lithium vanadyl phosphate: adding the above calcined LiOVPO4Adding agate beads into the precursor according to the ball-to-powder ratio of 10:1, performing ball milling refinement on the precursor powder for 350rpm/2h by using an agate grinding tank, and performing ball milling to obtain LiOVPO4The particle size of the precursor is about 700 nm.
Thinning LiOVPO4Precursor powder at 10% (volume fraction) O2And 90% N2The formed mixed gas is subjected to segmented sintering, the temperature is increased to 200 ℃ at the speed of 2 ℃/min, the constant temperature sintering is carried out for 2h, the temperature is increased to 550 ℃ at the speed of 1 ℃/min, the constant temperature sintering is carried out for 12h, and furnace cooling is carried out to obtain lithium vanadyl phosphate (LiOVPO)4) And (5) finishing.
(4) Preparation of ternary raw material/lithium vanadyl phosphate composite cathode material
Adding 11.3g of the obtained lithium vanadyl phosphate into 100g of alcohol, adding 3g of polyethylene glycol and 0.8g of super p, and stirring and dissolving for 1 h; obtaining a dispersion of the coating material;
100g of a Ni-Co-Mn ternary material Li (Ni) was weighed0.5Co0.2Mn0.3)O2(the average particle size is 13.9 microns), adding the solution into the solution, continuously stirring for 4 hours, centrifuging the obtained slurry at the rotating speed of 1000rpm for 0.5 hour, removing the supernatant, collecting the precipitate, and drying the obtained precipitate at 120 ℃ in vacuum for 1 hour to obtain the composite cathode material with a coating structure, namely the lithium nickel cobalt manganese oxide coated with the lithium vanadyl phosphate.
Through calculation, in the obtained cathode material, the mass ratio of lithium vanadyl phosphate to lithium nickel cobalt manganese oxide is 1: 8.8, the thickness of the coating layer (lithium iron vanadium phosphate) is 500 nm.
Example 4
A preparation method of a positive active material of a lithium ion battery comprises the following steps:
(1) preparing a lithium vanadium oxide phosphate precursor:
weighing 5.46g of vanadium pentoxide, 6.91g of ammonium dihydrogen phosphate and 25.11g of oxalic acid, dissolving in 400mL of deionized water, stirring in a 65 ℃ water bath kettle for 2.5h, and fully dissolving; then adding 2.33g of lithium carbonate and 2g of glucose, and continuously stirring for reaction for 10 hours to obtain mixed slurry; vacuum drying the obtained mixed slurry at 100 ℃ for 4h to obtain lithium vanadyl phosphate (LiVOPO)4) And (3) precursor.
(2)LiOVPO4Pre-sintering of a precursor: drying LiOVPO4Heating the precursor powder to 300 ℃ at the speed of 4 ℃/min under the protection of nitrogen atmosphere, and preserving heat for 2h to obtain the pre-sintered LiOVPO4And (3) precursor powder.
(3) Mixing the ternary raw material/lithium vanadyl phosphate precursor: 10.9g of calcined LiOVPO was added4Adding the precursor powder into 60g of alcohol, stirring and dissolving for 1h to obtain LiOVPO4A dispersion of a precursor;
100g of a Ni-Co-Mn ternary material Li (Ni) was weighed0.5Co0.2Mn0.3)O2(average particle diameter: 14.2 μm) was added to the above LiOVPO4Continuously stirring the alcohol dispersion liquid of the precursor for 1.5h, and drying the obtained slurry at 100 ℃ for 1h in vacuum to obtain mixed powder;
(4) preparation of ternary raw material/lithium vanadyl phosphate composite cathode material
Mixing the dried mixed powder with 10% O2+90％N2And (3) performing segmented sintering in the mixed atmosphere, namely heating to 200 ℃ at the speed of 2 ℃/min, sintering at the constant temperature for 2h, heating to 550 ℃ at the speed of 1 ℃/min, sintering at the constant temperature for 12h, and cooling along with a furnace to obtain the composite cathode material with a coating structure, namely the lithium nickel cobalt manganese oxide coated by the lithium vanadyl phosphate.
Through calculation, in the obtained cathode material, the mass ratio of lithium vanadyl phosphate to lithium nickel cobalt manganese oxide is 1: 19, the thickness of the coating layer (lithium vanadyl phosphate) was 650 nm. The lithium vanadyl phosphate layer is discontinuously attached to the surface of the nickel cobalt lithium manganate; the area coated by the lithium vanadyl phosphate layer accounts for 85% of the total surface area of the nickel cobalt lithium manganate.
To highlight the beneficial effects of the present invention, the following comparative examples are now set up for example 1:
comparative example 1
For Ni-Co-Mn ternary material Li (Ni)0.5Co0.2Mn0.3)O2No treatment is done.
Comparative example 2 ball milling mixing of ternary raw materials + lithium vanadium iron phosphate finished product (no addition of film agent and solvent):
100g of Ni-Co-Mn ternary material Li (Ni) is weighed0.5Co0.2Mn0.3)O2(the average particle size is 14.5 mu m), 6.4g of lithium iron vanadium phosphate finished product (the average particle size is 500-600nm), adding agate beads according to the ball-powder ratio of 10:1, performing ball milling and mixing on the mixed powder for 300rpm/2h by using an agate grinding tank, and sieving by using a 300-mesh sieve after ball milling to obtain the cathode material.
Comparative example 3 stirring and mixing of ternary raw material + lithium vanadyl phosphate finished product:
100g of Ni-Co-Mn ternary material Li (Ni) is weighed0.5Co0.2Mn0.3)O2(average particle size of 14.5 μm), 6.4g of lithium vanadyl phosphate finished product (average particle size of 500-600nm), adding 150mL of deionized water as solvent for dissolution, magnetically stirring at 25 ℃ for 300rpm/2h, then vacuum drying at 120 ℃ for 1h, and sieving through a 300-mesh sieve to obtain the cathode material.
The batteries manufactured using the cathode materials of examples 1 to 4 and the batteries manufactured in comparative examples 1 to 3 were subjected to performance tests, and the results are shown in table 1 below.
TABLE 1
Figure BDA0001372237510000141
Wherein, the exothermic amount (J/g) in the above Table 1 is obtained by testing the stability by DSC method (differential scanning calorimetry). Thermal stability is a basic problem of the safety of lithium ion batteries, the safety of the batteries is mainly related to the thermal activity of electrode materials, generally, the battery temperature is considered to rise, a plurality of exothermic reactions occur inside the battery, and when the generated heat exceeds the dissipation of the heat, the battery is thermally out of control. DSC (is a measure of the relationship between the temperature of a thermal transition inside a material and the heat flow.
The electrode sheets of the above examples 1-3 and comparative examples 1-3 were assembled into CR2025 button cells, charged to 4.3V at 1C rate at room temperature, the cells were taken off, the cells were disassembled in an Ar glove box, the active material on the positive current collector was peeled off, the mass was weighed, placed in an aluminum crucible and sealed, then taken out and placed in a DSC apparatus for DSC test under nitrogen protection at a temperature range of 30-500 ℃ at a temperature rate of 5 ℃/min, and the test results are shown in fig. 6. The exothermic amount (J/g) of each sample was calculated from the curve of FIG. 6.
As can be seen from table 1, the coated positive electrode material prepared according to the present invention has good processability, exhibits a higher specific capacity during discharge, and has a high median voltage during discharge, resulting in a higher energy density, compared to the conventional comparative example. The anode material is tightly coated, the structure is good, the surface layer is prevented from being in direct contact with electrolyte, the corrosion is reduced, and the circulation stability is improved. The thermal stability after coating is also obviously improved.
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 present 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 (8)

1. The lithium ion battery positive electrode material is characterized by comprising nickel cobalt lithium manganate and a coating layer arranged on the surface of the nickel cobalt lithium manganate, wherein the coating layer is made of lithium vanadium iron phosphate or lithium vanadium oxygen phosphate; the voltage platform of the nickel cobalt lithium manganate is 3.6-3.8V, and the iron phosphateThe voltage platform of the vanadium lithium is 3.6-3.7V, and the voltage platform of the lithium vanadyl phosphate is 3.8-3.9V; the thickness of the coating layer is 200-700 nm; the material of the coating layer is discontinuously and uniformly attached to the surface of the nickel cobalt lithium manganate, the coating area of the coating layer accounts for 85-95% of the total surface area of the nickel cobalt lithium manganate, and the compacted density of the anode material of the lithium ion battery is 3.5-3.7g/cm3。
2. The positive electrode material of the lithium ion battery of claim 1, wherein the mass ratio of the material of the coating layer to the nickel cobalt lithium manganate is 1: (5.7-19).
3. A preparation method of a lithium ion battery anode material is characterized by comprising the following steps:
providing a coating layer material, wherein the coating layer material is lithium vanadium iron phosphate or lithium vanadyl phosphate;
adding a first solvent and a film-forming agent into the coating material, uniformly mixing to obtain a dispersion liquid of the coating material, adding nickel cobalt lithium manganate, mixing for 0.5-4h, drying the obtained mixture at 90-160 ℃ in vacuum, and sieving the dried solid with a 300-mesh 400-mesh sieve to obtain the lithium ion battery anode material;
the lithium ion battery positive electrode material comprises nickel cobalt lithium manganate and a coating layer arranged on the surface of the nickel cobalt lithium manganate; the thickness of the coating layer is 200-700 nm; the film forming agent comprises at least one of polyvinyl alcohol, polyethylene glycol, polyvidone, sodium dodecyl benzene sulfonate and stearic acid; the voltage platform of the nickel cobalt lithium manganate is 3.6-3.8V, the voltage platform of the lithium vanadium iron phosphate is 3.6-3.7V, and the voltage platform of the lithium vanadium oxygen phosphate is 3.8-3.9V; the coating layer is discontinuously attached to the surface of the nickel cobalt lithium manganate, the coating area of the coating layer accounts for 85-95% of the total surface area of the nickel cobalt lithium manganate, and the compacted density of the lithium ion battery anode material is 3.5-3.7g/cm3。
4. The method for preparing the positive electrode material of the lithium ion battery according to claim 3, wherein the coating material is prepared by the following steps: providing a coating material precursor, presintering the coating material precursor at the constant temperature of 200-400 ℃ for 2-4h under protective gas, then carrying out ball milling on the presintered coating material precursor, and sintering the ball-milled coating material precursor; wherein, the sintering process comprises the following steps: the temperature is raised to 250 ℃ for 150-.
5. The method for preparing the positive electrode material of the lithium ion battery according to claim 4, wherein when the cladding material is lithium vanadium iron phosphate, the preparation process of the precursor of the cladding material is as follows: lithium source, vanadium source, iron source and phosphorus source are mixed according to the mol ratio of Li: fe: v: p is 1: a: b: 1, adding a second solvent and a complexing agent, mixing and dispersing to obtain a mixed slurry, adjusting the pH of the mixed slurry to 1-7, and performing vacuum drying on the obtained mixed slurry at 90-160 ℃ to obtain a lithium vanadium iron phosphate precursor; wherein 0 < a < 1, 0 < b < 2/3, and 2a +3b 2.
6. The method for preparing the positive electrode material of the lithium ion battery according to claim 4, wherein when the coating material is lithium vanadyl phosphate, the preparation process of the coating material precursor is as follows: mixing a lithium source, a vanadium source, a phosphorus source and a second solvent with a complexing agent and/or a reducing agent, stirring in a water bath at 65-100 ℃ to obtain mixed slurry, and carrying out vacuum drying on the mixed slurry at 90-160 ℃ to obtain the lithium vanadyl phosphate precursor.
7. A preparation method of a lithium ion battery anode material is characterized by comprising the following steps:
providing a coating material precursor, wherein the coating material precursor is a lithium iron vanadium phosphate precursor or a lithium vanadyl phosphate precursor; presintering the coating material precursor at the constant temperature of 200-400 ℃ for 2-4h under protective gas, and cooling to obtain a presintered coating material precursor;
dissolving the presintered coating material precursor in a water-soluble polar solvent, adding nickel cobalt lithium manganate into the water-soluble polar solvent, mixing for 0.5 to 10 hours to obtain first slurry, and drying the first slurry at 90 to 160 ℃ in vacuum to obtain a positive electrode material precursor;
sintering the precursor of the positive electrode material, wherein the sintering process comprises the following specific steps: firstly heating to 250 ℃ for 150-; after cooling, sieving the solid obtained by sintering by a sieve of 300-;
the lithium ion battery positive electrode material comprises nickel cobalt lithium manganate and a coating layer arranged on the surface of the nickel cobalt lithium manganate; the thickness of the coating layer is 200-700 nm; the voltage platform of the nickel cobalt lithium manganate is 3.6-3.8V, the voltage platform of the lithium vanadium iron phosphate is 3.6-3.7V, and the voltage platform of the lithium vanadium oxygen phosphate is 3.8-3.9V; the coating layer is discontinuously attached to the surface of the nickel cobalt lithium manganate, the coating area of the coating layer accounts for 85-95% of the total surface area of the nickel cobalt lithium manganate, and the compacted density of the lithium ion battery anode material is 3.5-3.7g/cm3。
8. A lithium ion battery comprising the lithium ion battery positive electrode material according to any one of claims 1 to 2.
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