CN112531147A - Positive active material and preparation method and application thereof - Google Patents

Positive active material and preparation method and application thereof Download PDF

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Publication number
CN112531147A
CN112531147A CN202011401500.8A CN202011401500A CN112531147A CN 112531147 A CN112531147 A CN 112531147A CN 202011401500 A CN202011401500 A CN 202011401500A CN 112531147 A CN112531147 A CN 112531147A
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active material
gas
coating
positive electrode
electrode active
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曾家江
伍鹏
李素丽
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Zhuhai Cosmx Battery Co Ltd
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Zhuhai Cosmx Battery 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
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
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  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a positive active material and a preparation method and application thereof. The method comprises four steps: firstly, introducing a first coating material source, and carrying out physical adsorption on pores and surfaces of positive active materials; introducing gas which does not react with the first coating material source for cleaning, and removing byproducts and redundant first coating material source; thirdly, introducing a second coating material source, and reacting the second coating material source with the pores of the positive active material and the adsorbed first coating material source on the surface to generate a film type coating layer; and fourthly, introducing inert gas for cleaning. The method can improve the storage performance of the high-water-absorption positive active material and reduce the harmful effects of moisture and carbon dioxide in the air on the positive active material; the method is to reduce the high dependence of the high-hygroscopicity positive active substance on the environmental humidity by using a low-temperature atomic deposition technology.

Description

Positive active material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a positive active material, and a preparation method and application thereof.
Background
At present, commercial lithium ion batteries are mainly divided into two main categories, namely 3C digital lithium ion batteries and power batteries, wherein the demand of the 3C digital lithium ion batteries on energy density is unprecedentedly close to 800Wh/L, and the demand of the 3C digital lithium ion batteries on high-voltage single-crystal LiCoO2The compacted density can reach 4.2g/cm2But LiCoO is the mainstream of the market2The storage capacity is lower than 4.45V and is about 180mAh/g, the safety and the overcharge resistance are poor, Co belongs to rare resources and is expensive, and meanwhile, the metal cobalt easily causes pollution to the environment. And LiNiO2The capacity of more than 200mAh/g can be exerted under the voltage of 4.2V, but the thermal stability is poor, the safety problem is easy to cause, the synthesis is needed in an oxygen atmosphere, cation mixing and a compound with a non-stoichiometric structure are easy to generate, and the consistency, the safety and the like of the battery are greatly challenged.
LiCoO is synthesized by positive active material nickel-cobalt-manganese oxide system2Good cycle performance, LiNiO2High specific capacity and the like, and has better application prospect. However, the nickel-cobalt-manganese oxide system is very easy to adsorb water in the air, and the nickel-cobalt-manganese oxide system does not simply absorb water physically, but can react with the absorbed water chemically, so that the original surface property of the material is changed. For example, a series of chemical reactions occur during water absorption:
4LiMO2+H2O→4MO+4LiOH+O2(M＝NixCoyMn1-x-y，x＞0,y＞0,x+y＜1)
2LiOH+CO2→Li2CO3+H2O
LiOH+H2O→LiOH·H2O
after the reaction, trace amounts of crystal water, free water and carbonate are generated on the surface of the positive active material, which can cause great non-reversible changes in the electrochemical properties of the positive active material.
Firstly, the water molecules, carbon dioxide in the air and the positive electrode active material act together to form a relatively thick non-conductive carbonate and non-conductive transition metal oxide composite film layer. The carbonate can further increase the pH value of the anode active material, so that the gel phenomenon is easy to occur in the anode pulping process, the smooth proceeding of the subsequent coating process is influenced, and the performance of the battery is further influenced. The non-conductive transition metal oxide composite film layer can lead to the inactivation of the partially coated positive active material and can not participate in the charging and discharging process, thus leading to the reduction of the specific capacity of the positive active material. Meanwhile, a part of carbonate can be decomposed to generate gas in the charging and discharging processes, and the swelling of the battery is caused. In addition, trace amount of water carried in the positive active material may be mixed with lithium salt such as LiPF in the electrolyte after injection into the electrolyte6Reactions occur which lead to electrolyte destruction, reaction to form HF, and corrosion of the positive electrode active material, which leads to rapid degradation of the cycling performance of the material.
In recent years, researchers have attempted various methods for reducing the moisture absorption sensitivity of a positive electrode active material, such as coating a non-water-absorbing oxide material on the surface of the positive electrode active material, coating the surface of the positive electrode active material with a solid acid, reducing the surface residual alkali by performing a partial neutralization reaction by heat treatment, and annealing after removing the surface residual alkali by washing with water. These works have improved the reduction of the water absorption of the positive active material, but the water content of the final cell is still much higher than that of the electrode sheet of lithium cobaltate in the same environment. The main reasons for this are two points: firstly, the nano-scale particles are coated on the surface of a micron scale by adopting the traditional solid phase powder coating, and the coating uniformity and consistency are difficult to control. Island-shaped particles are easy to form after liquid phase coating, and uniform coating is difficult to realize. And in the preparation process of the battery core, trace moisture and carbon dioxide in the environment cannot be thoroughly controlled, the electrode plate is exposed in the environment from the beginning of coating until electrolyte is injected, the exposure time is long in the process and the contact surface with air is large, and the electrode plate is very easy to absorb moisture and carbon dioxide in the air and react.
At present, in order to reduce the contact of the positive active material with moisture and carbon dioxide in the air, a high-power dehumidifier is generally adopted in the industry to reduce the humidity of the production environment to be below 2%, but the cost is very high and the cost is 10000m2For a 3m (high) plant, the annual expenditure of electricity alone is up to several thousand yuan.
This inevitably hinders the progress of development of the positive electrode active material, and therefore, it is urgently required to provide a method for producing a positive electrode active material capable of improving the storage property of a high water-absorbing positive electrode active material and reducing the harmful effects of moisture and carbon dioxide in the air on the positive electrode active material.
Disclosure of Invention
The invention provides a positive active substance and a preparation method and application thereof, the positive active substance can overcome the defect that the electrochemical performance of the final battery is influenced by the reaction of the existing high-water-absorption positive active substance with trace moisture and carbon dioxide in the air, and the method reduces the high dependence of the high-water-absorption positive active substance on the environmental humidity by using a low-temperature atomic deposition technology, can improve the storage performance of the high-water-absorption positive active substance, and reduces the harmful influence of the moisture and the carbon dioxide in the air on the positive active substance.
According to the invention, the surface of the positive active material is coated with the inert coating layer through atomic or molecular deposition, and the coated inert coating layer can reduce the chance that the positive active material is in direct contact with moisture and carbon dioxide in the air, so that the requirement of the positive active material on the environment required by the preparation process is reduced; the arrangement of the coated inert coating layer can effectively reduce the sensitivity of the positive active material to moisture and carbon dioxide in the key working procedures, save the cost for obtaining a severe production environment, and most importantly, reduce the occurrence of side reactions of the positive active material, so that the loss of metal cation mixing and circulation performance in the assembled lithium ion battery is reduced, thereby improving the comprehensive performance of the battery.
The purpose of the invention is realized by the following technical scheme:
the positive electrode active material is characterized in that a coating layer is coated on the surface and/or in pores of the positive electrode active material, the coating layer is an oxide coating layer or a nitride coating layer, and the coating layer is obtained after a first coating material source and a second coating material source react.
According to the invention, the thickness of the coating is < 10nm, for example < 5nm or < 2nm or 2-5nm or 1-2nm or < 1nm, also for example 0.1-1 nm.
According to the invention, the first coating substance source is an organometallic compound or a metal halide; for example, the organometallic compound is selected from at least one of trimethylaluminum, triethylaluminum, triethoxyaluminum, trimethylborane, triethylborane, diborane, titanium triisopropoxide, titanium tetraethoxide, titanium tetraisopropoxide, zirconium tetra-tert-butoxide, trimethylmagnesium, triethylmagnesium, tantalum pentaethoxide, trimethylzinc, or triethylzinc; the metal halide is selected from at least one of aluminum tribromide, aluminum trichloride, boron tribromide, titanium tetraiodide, titanium tetrachloride, zirconium tetraiodide and tantalum pentachloride.
According to the present invention, the second coating material source is a gas capable of reacting with the first coating material source to produce an oxide or a nitride, or a substance capable of being atomized or vaporized by a treatment capable of reacting with the first coating material source to produce an oxide or a nitride, or a plasma gas capable of reacting with the first coating material source to produce an oxide or a nitride.
For example, the gas is selected from water (H)2O), ozone (O)3) Oxygen (O)2) (ii) a The substance capable of atomizing or gasifying after treatment is selected from hydrogen peroxide (H)2O2) Methanol (CH)3OH) or ethanol (CH)3CH2OH); the plasma gas is selected from ozone (O)3) Oxygen (O)2) Ammonia (NH)3) Helium (He), hydrogen (H)2) Argon (Ar), neon (Ne), and water (H)2O), Nitric Oxide (NO), tetrafluoromethane (CF)4) Hexafluoroethane (C)2F6) Carbon dioxide (CO)2)。
The invention also provides a preparation method of the positive active material, which comprises the following steps:
s1) placing the positive active substance into a reaction chamber of atomic layer deposition equipment filled with inert gas in advance, and preserving heat;
s2) introducing a first coating substance source into a reaction chamber of the atomic layer deposition equipment, wherein the first coating substance source is adsorbed on the pores and the surface of the positive active material; introducing gas which does not react with the first coating substance source into a reaction chamber of the atomic layer deposition equipment;
s3) introducing a second coating substance source into a reaction chamber of the atomic layer deposition equipment, wherein the second coating substance chemically reacts with the first coating substance source adsorbed on the pores and the surface of the positive electrode active substance to form a coating layer; introducing inert gas into a reaction chamber of the atomic layer deposition equipment;
s4) repeating the steps S2) and S3) at least once, to obtain the positive electrode active material having a coating layer on the surface.
In some embodiments, in step S1), the positive electrode active material is selected from a lithium nickel cobalt manganese oxide-based positive electrode active material (Li)zNixCoyMn1-x-yO2Wherein z is more than or equal to 0.95 and less than or equal to 1.05, x>0，y>0，x+y<1) Lithium nickel cobalt aluminate-based positive electrode active material (Li)zNixCoyAl1-x-yO2Wherein z is more than or equal to 0.95 and less than or equal to 1.05, x>0，y>0，0.8≤x+y<1) Lithium nickel cobalt manganese aluminate positive electrode active material (Li)zNixCoyMnwAl1-x-y-wO2Wherein, z is more than or equal to 0.95 and less than or equal to 1.05, x>0，y>0，w>0，0.8≤x+y+w<1)。
Illustratively, the positive electrode active material is selected from LiNi1/3Co1/3Mn1/3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.4Co0.2Mn0.4O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2、LiNi0.7Co0.2Mn0.1O2And LiNi0.7Co0.15Mn0.15O2At least one of (1).
In some embodiments, the method further comprises the steps of:
s0) heat-treating the positive electrode active material.
In some embodiments, in step S0), the temperature of the heat treatment is 60 to 350 ℃, the time of the heat treatment is not particularly limited, and the temperature of the positive electrode active material may be a desired temperature, and the time of the heat treatment is, for example, 2h or less; the heat treatment atmosphere used for the heat treatment is oxygen, dry air, or a gas that does not react with the positive electrode active material. The purpose of the heat treatment is to raise the temperature of the positive electrode active material to be equal to or the same as the temperature of the first cladding material source, which facilitates uniform filling of the first cladding material source gas molecules.
In some embodiments, in step S1), the atomic layer deposition apparatus is an atomic layer deposition apparatus commonly used in the art, and may be obtained after being purchased commercially, for example.
In some embodiments, in step S1), the temperature in the reaction chamber of the atomic layer deposition apparatus is 60-350 ℃, i.e., the temperature of the incubation; for example, 60 ℃, 80 ℃, 100 ℃, 120 ℃, 150 ℃, 180 ℃, 200 ℃, 250 ℃, 280 ℃, 300 ℃, 340 ℃, 350 ℃.
In some embodiments, in step S1), the time of the incubation is not particularly defined, and it is sufficient to ensure that the temperature in the reaction chamber of the atomic layer deposition apparatus is constant, and the temperature in the reaction chamber of the atomic layer deposition apparatus is the same as or similar to the temperature of the positive active material.
In some embodiments, in step S1), the inert gas is at least one of nitrogen, argon and helium.
In step 2) of the present invention, the first coating material source is adsorbed on the pores and the surface of the positive electrode active material in a gaseous adsorption manner.
In some embodiments, in step S2), the first coating substance source is an organometallic compound or a metal halide; for example, the organometallic compound is selected from at least one of trimethylaluminum, triethylaluminum, triethoxyaluminum, trimethylborane, triethylborane, diborane, titanium triisopropoxide, titanium tetraethoxide, titanium tetraisopropoxide, zirconium tetra-tert-butoxide, trimethylmagnesium, triethylmagnesium, tantalum pentaethoxide, trimethylzinc, or triethylzinc; the metal halide is selected from at least one of aluminum tribromide, aluminum trichloride, boron tribromide, titanium tetraiodide, titanium tetrachloride, zirconium tetraiodide and tantalum pentachloride.
In some embodiments, in step S2), the flow rate and the time for introducing the first coating material source are not particularly defined, and may be reasonably adjusted according to the volume of the reaction chamber of the ald apparatus and the size of the positive active material, so as to ensure that the introduction amount (the product of the flow rate and the time for introducing the first coating material source) of the first coating material source is greater than the saturation amount for the pores and the surface of the positive active material capable of adsorbing the first coating material source.
Illustratively, the first coating species source is introduced at a flow rate of 1-100sccm, such as 1sccm, 2sccm, 5sccm, 8sccm, 10sccm, 15sccm, 20sccm, 30sccm, 50sccm, 60sccm, 80sccm, 100 sccm.
Illustratively, the first coating substance source is passed for a time of 1ms to 100s, such as 1ms, 5ms, 10ms, 50ms, 100ms, 200ms, 500ms, 1s, 2s, 5s, 10s, 20s, 50s, 80s, 100 s.
In some embodiments, in step S2), the first coating substance source may be separately introduced into the reaction chamber of the atomic layer deposition apparatus, or may be introduced into the reaction chamber of the atomic layer deposition apparatus together with a carrier gas, where the carrier gas may be at least one of argon, nitrogen, or helium.
In some embodiments, the first coating substance sources selected in the repeated step S2) may be the same or different, the flow rates of the first coating substance sources may be the same or different, the time periods of the first coating substance sources may be the same or different, and the amounts of the first coating substance sources may be the same or different.
In step S2), a gas that does not react with the first coating material source is introduced into the reaction chamber of the ald apparatus for cleaning, and the excess first coating material source in the reaction chamber of the ald apparatus is removed.
In some embodiments, the gas that is non-reactive with the first coating substance source in step S2) is selected from at least one of argon, nitrogen, or helium.
In some embodiments, in step S2), the flow rate and the time for introducing the gas that is not reactive with the first coating material source are not particularly defined, and may be reasonably adjusted according to the volume of the reaction chamber of the ald apparatus, the size of the positive active material, and the introduction amount of the first coating material source, so as to ensure that the introduction of the gas that is not reactive with the first coating material source can take away the excessive first coating material source in the reaction chamber of the ald apparatus.
Illustratively, the gas that is not reactive with the first cladding material source is introduced at a flow rate of 1-100sccm, such as 1sccm, 2sccm, 5sccm, 8sccm, 10sccm, 15sccm, 20sccm, 30sccm, 50sccm, 60sccm, 80sccm, or 100 sccm.
Illustratively, the gas that is non-reactive with the first coating substance source is passed for a time period, i.e. for purging, of 1ms to 100s, for example 1ms, 5ms, 10ms, 50ms, 100ms, 200ms, 500ms, 1s, 2s, 5s, 10s, 20s, 50s, 80s or 100 s.
In some embodiments, the gas selected in step S2) of the repeating operation may be the same or different, the flow rate of the gas that is not reactive with the first coating material source may be the same or different, and the flow time of the gas that is not reactive with the first coating material source may be the same or different.
In some embodiments, in step S3), the second coating material source is a gas that can react with the first coating material source to form an oxide or a nitride, or a material that can react with the first coating material source to form an oxide or a nitride and can be atomized or gasified after being processed, or a plasma gas that can react with the first coating material source to form an oxide or a nitride.
For example, the gas is selected from water (H)2O), ozone (O)3) Oxygen (O)2) (ii) a The substance capable of atomizing or gasifying after treatment is selected from hydrogen peroxide (H)2O2) Methanol (CH)3OH) or ethanol (CH)3CH2OH); the plasma gas is selected from ozone (O)3) Oxygen (O)2) Ammonia (NH)3) Helium (He), hydrogen (H)2) Argon (Ar), neon (Ne), and water (H)2O), Nitric Oxide (NO), tetrafluoromethane (CF)4) Hexafluoroethane (C)2F6) Carbon dioxide (CO)2)。
In some embodiments, in step S3), the flow rate and time for introducing the second coating material source are not particularly defined, and may be reasonably adjusted according to the volume of the reaction chamber of the ald apparatus, the size of the positive active material, and the introduction amount of the first coating material source, so as to ensure that the introduction amount of the second coating material source (the product of the flow rate and time for introducing the second coating material source) can react with the pores of the positive active material and the surface-adsorbed first coating material source.
Illustratively, the second coating material source is introduced at a flow rate of 1-100sccm, such as 1sccm, 2sccm, 5sccm, 8sccm, 10sccm, 15sccm, 20sccm, 30sccm, 50sccm, 60sccm, 80sccm, or 100 sccm.
Illustratively, the second coating substance source is provided for an access time, i.e. the second specified time, of 1ms to 100s, such as 1ms, 5ms, 10ms, 50ms, 100ms, 200ms, 500ms, 1s, 2s, 5s, 10s, 20s, 50s, 80s or 100 s.
In some embodiments, in step S3), the second coating material source may be separately introduced into the reaction chamber of the atomic layer deposition apparatus, or may be introduced into the reaction chamber of the atomic layer deposition apparatus together with a carrier gas, where the carrier gas may be at least one of argon, nitrogen, or helium.
In some embodiments, the second coating substance source selected in step S3) of the repeating operation may be the same or different, the flow rate of the second coating substance source may be the same or different, the time of the second coating substance source may be the same or different, and the amount of the second coating substance source may be the same or different.
In step S3), the inert gas is introduced into the reaction chamber of the ald apparatus for cleaning, so as to remove the excess second coating material source and by-products in the reaction chamber of the ald apparatus.
In some embodiments, in step S3), the inert gas is selected from nitrogen or argon.
In some embodiments, in step S3), the flow rate and time of the inert gas are not particularly defined, and may be reasonably adjusted according to the volume of the reaction chamber of the atomic layer deposition apparatus, the size of the positive active material, and the introduction amount of the second coating material source, so as to ensure that the inert gas can introduce the excess second coating material source and the by-products away from the reaction chamber of the atomic layer deposition apparatus.
Illustratively, the inert gas is introduced at a flow rate of 1-100sccm, such as 1sccm, 2sccm, 5sccm, 8sccm, 10sccm, 15sccm, 20sccm, 30sccm, 50sccm, 60sccm, 80sccm, or 100 sccm.
The inert gas is introduced, for example, for a period of time of 1ms to 100s, for example, 1ms, 5ms, 10ms, 50ms, 100ms, 200ms, 500ms, 1s, 2s, 5s, 10s, 20s, 50s, 80s, or 100 s.
In some embodiments, the inert gas selected in the step S3) of repeating the operation may be the same or different, the flow rate of the inert gas may be the same or different, and the time of the inert gas may be the same or different.
In some embodiments, step S4), steps S2) and S3) are repeated 1-100 times.
In some embodiments, the pressure of the reaction chamber of the atomic layer deposition apparatus is 1Pa to 2kPa, preferably 1Pa to 1kPa, for example 1Pa to 2 Pa. The smaller the pressure of the reaction chamber of the atomic layer deposition equipment is, namely the higher the vacuum degree is, the more favorable the adsorption and reaction of the first coating substance source and the second coating substance source on the surface of the positive active material are.
In the present invention, atomic deposition (ALD) is not a continuous process, but consists of a series of half-reactions, each unit cycle of which comprises the following four steps: firstly, introducing a first coating material source, and carrying out physical adsorption on pores and surfaces of positive active materials; introducing gas which does not react with the first coating material source for cleaning, and removing byproducts and redundant first coating material source; thirdly, introducing a second coating material source, and reacting the second coating material source with the pores of the positive active material and the adsorbed first coating material source on the surface to generate a film type coating layer; and fourthly, introducing inert gas for cleaning. After one unit cycle, a layer of film-shaped oxide or nitride coating is formed on the pores and the surface of the positive electrode active material, and the coating is obtained by growing layer by layer on the surface and in the pores of the positive electrode active material, so that the harmful reaction of the positive electrode active material with moisture and carbon dioxide in the air is weakened.
In some embodiments, the coating of the same species may be performed as required in steps S2) and S3); for example:
(1) the first coating material source is trimethylaluminum and the second coating material source is H2When O is present, Al is obtained2O3And (4) coating.
(2) The first source of coating material is titanium tetrachloride and the second source of coating material is H2When O is present, TiO is obtained2And (4) coating.
(3) The first coating material source is trimethyl aluminum and titanium tetrachloride, and the second coating material source is H2O, repeating the operation for a plurality of times to obtain the anode active material-Al2O3-TiO2TiO positive electrode active material2-Al2O3And a positive electrode active material-Al2O3-TiO2-Al2O3And the like in various combinations.
In some embodiments, the coating has a thickness of ≦ 10nm, such as ≦ 5nm or ≦ 2nm or 2-5nm or 1-2nm or ≦ 1nm, and further such as 0.1-1 nm.
In some embodiments, the coating layer is coated on the surface and/or in the pores of the positive electrode active material.
The invention also provides the positive active material prepared by the method.
The invention also provides a positive plate which comprises the positive active material.
In some embodiments, the positive electrode sheet includes a positive electrode active material layer including the positive electrode active material described above.
The invention also provides a lithium ion battery which comprises the positive electrode active material.
The invention also provides a lithium ion battery which comprises the positive plate.
The invention has the beneficial effects that:
the invention provides a positive active material and a preparation method and application thereof. The cathode active material can overcome the defect that the electrochemical performance of the final battery is influenced by the reaction of the existing high-water-absorption cathode active material with trace moisture and carbon dioxide in the air, and the method can improve the storage performance of the high-water-absorption cathode active material and reduce the harmful influence of the moisture and the carbon dioxide in the air on the cathode active material; the method is to reduce the high dependence of the high-hygroscopicity positive active substance on the environmental humidity by using a low-temperature atomic deposition technology. However, the conventional positive electrode active material can react with a trace amount of moisture and carbon dioxide in the air, and for example, when the positive electrode active material is placed in an environment containing a trace amount of moisture and carbon dioxide, the self weight of the positive electrode active material increases and then becomes stable along with the contact reaction with the carbon dioxide and the moisture in the air. Although the positive active material of the invention is coated and modified, the phenomenon that the weight of the positive active material is increased and then becomes stable along with the contact reaction of the positive active material with carbon dioxide and moisture in the air also occurs, the weight increase percentage of the positive active material is far lower than that of the positive active material without coating treatment, and the time for achieving the stability is also greatly shortened.
Drawings
FIG. 1 shows the results of example 1 of the present inventionAl2O3And SEM images of the surface and the section of the crushed coated polycrystalline secondary spherical particles of the ternary cathode material.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1
Reacting LiNi0.83Co0.12Mn0.05O2The positive electrode active material is placed in a reaction chamber of an atomic layer deposition device filled with dry air in advance, the reaction chamber also contains a plasma generating device and can be separated from the reaction chamber, and the cavity and the reaction chamber can be communicated through a valve when necessary. After the positive active substance is placed, vacuumizing to 1-2Pa, raising the temperature of the reaction chamber, and finally keeping the temperature of the reaction chamber at 80 +/-1 ℃.
(1) Introducing trimethylaluminum gas into the reaction chamber by taking nitrogen as a carrier, and controlling the introduction flow of the trimethylaluminum gas to be 10sccm for 0.1 s; and then introducing nitrogen into the reaction chamber to clean for 5s, taking away the surplus trimethyl aluminum in the reaction chamber, and maintaining the air pressure in the reaction chamber at 1-2Pa after cleaning.
(2) Opening plasma generation equipment and a plasma cavity, introducing plasma oxygen into the reaction chamber, and controlling the introduction flow of the plasma oxygen to be 10sccm for 1 s; and then introducing nitrogen into the reaction chamber for cleaning for 5s, taking away excess plasma oxygen and byproducts in the reaction chamber, and maintaining the air pressure in the reaction chamber at 1-2Pa after cleaning.
(3) Introducing trimethylaluminum gas into the reaction chamber by taking nitrogen as a carrier, and controlling the introduction flow of the trimethylaluminum gas to be 10sccm for 1 s; and then introducing nitrogen into the reaction chamber to clean for 5s, taking away the surplus trimethylaluminum gas in the reaction chamber, and maintaining the air pressure in the reaction chamber at 1-2Pa after cleaning.
(4) Opening plasma generation equipment and a plasma cavity, introducing plasma oxygen into the reaction chamber, and controlling the introduction flow of the plasma oxygen to be 10sccm for 1 s; and then introducing nitrogen into the reaction chamber for cleaning for 5s, taking away excess plasma oxygen and byproducts in the reaction chamber, and maintaining the air pressure in the reaction chamber at 1-2Pa after cleaning.
Repeating the steps (1) to (4) for 10 times to obtain Al with the thickness less than or equal to 2nm2O3The positive active material of the coating layer realizes the preparation of the surface coating modified positive active material of the positive active material at the low temperature of 80 ℃.
Example 2
Reacting LiNi0.83Co0.12Mn0.05O2Placing the positive active substance in a reaction chamber of an atomic layer deposition device filled with dry air in advance as a positive active material, vacuumizing to 1-2Pa after the positive active substance is placed, raising the temperature of the reaction chamber, and finally keeping the temperature of the reaction chamber at 150 +/-1 ℃.
(1) Introducing trimethylaluminum gas into the reaction chamber by taking nitrogen as a carrier, and controlling the introduction flow of the trimethylaluminum gas to be 10sccm for 0.1 s; and then introducing nitrogen into the reaction chamber to clean for 5s, taking away the surplus trimethyl aluminum in the reaction chamber, and maintaining the air pressure in the reaction chamber at 1-2Pa after cleaning.
(2) Introducing steam into the reaction chamber by taking nitrogen as a carrier, and controlling the introduction flow of the steam to be 10sccm for 1 s; and then introducing nitrogen into the reaction chamber to clean for 5s, taking away excessive water vapor and byproducts in the reaction chamber, and maintaining the air pressure in the reaction chamber at 1-2Pa after cleaning.
(3) Introducing trimethylaluminum gas into the reaction chamber by taking nitrogen as a carrier, and controlling the introduction flow of the trimethylaluminum gas to be 10sccm for 2 s; and then introducing nitrogen into the reaction chamber to clean for 5s, taking away the surplus trimethyl aluminum in the reaction chamber, and maintaining the air pressure in the reaction chamber at 1-2Pa after cleaning.
(4) Introducing steam into the reaction chamber by taking nitrogen as a carrier, and controlling the introduction flow of the steam to be 10sccm for 1 s; and then introducing nitrogen into the reaction chamber for cleaning for 10s, taking away excessive water vapor and byproducts in the reaction chamber, and maintaining the air pressure in the reaction chamber at 1-2Pa after cleaning.
Repeating the steps (1) to (4) for 10 times to obtain Al with the thickness less than or equal to 2nm2O3The positive active material of the coating layer realizes the preparation of the positive active material with the surface coated and modified at the temperature of 150 ℃.
Example 3
The difference from embodiment 1 is that:
the positive electrode active material in the positive electrode active material is LiNi0.7Co0.15Mn0.15O2To obtain Al with the thickness less than or equal to 2nm2O3A positive electrode active material of the coating layer.
Example 4
The difference from embodiment 1 is that:
the positive electrode active material in the positive electrode active material is LiNi0.88Co0.05Mn0.07O2To obtain Al with the thickness less than or equal to 2nm2O3A positive electrode active material of the coating layer.
Example 5
Reacting LiNi0.88Co0.05Mn0.07O2Placing the positive active substance in a reaction chamber of an atomic layer deposition device filled with dry air in advance as a positive active material, vacuumizing to 1-2Pa after the positive active substance is placed, raising the temperature of the reaction chamber, and finally keeping the temperature of the reaction chamber at 150 +/-1 ℃.
(1) Introducing trimethylaluminum gas into the reaction chamber by taking nitrogen as a carrier, and controlling the introduction flow of the trimethylaluminum gas to be 10sccm for 0.1 s; and then introducing nitrogen into the reaction chamber to clean for 5s, taking away the surplus trimethyl aluminum in the reaction chamber, and maintaining the air pressure in the reaction chamber at 1-2Pa after cleaning.
(2) Introducing steam into the reaction chamber by taking nitrogen as a carrier, and controlling the introduction flow of the steam to be 10sccm for 1 s; and then introducing nitrogen into the reaction chamber to clean for 5s, taking away excessive water vapor and byproducts in the reaction chamber, and maintaining the air pressure in the reaction chamber at 1-2Pa after cleaning.
(3) Introducing trimethylaluminum gas into the reaction chamber by taking nitrogen as a carrier, and controlling the introduction flow of the trimethylaluminum gas to be 10sccm for 2 s; and then introducing nitrogen into the reaction chamber to clean for 5s, taking away the surplus trimethyl aluminum in the reaction chamber, and maintaining the air pressure in the reaction chamber at 1-2Pa after cleaning.
(4) Introducing steam into the reaction chamber by taking nitrogen as a carrier, and controlling the introduction flow of the steam to be 10sccm for 1 s; and then introducing nitrogen into the reaction chamber for cleaning for 10s, taking away excessive water vapor and byproducts in the reaction chamber, and maintaining the air pressure in the reaction chamber at 1-2Pa after cleaning.
Repeating the steps (1) to (4) for 10 times to obtain Al with the thickness less than or equal to 2nm2O3A positive electrode active material of the coating layer.
Comparative example 1
LiNi without any treatment0.83Co0.12Mn0.05O2As a positive electrode active material.
Comparative example 2
Reacting LiNi0.83Co0.12Mn0.05O2With Al2O3Mixing the nanoparticles (the Al element addition amount is 0.01% of the addition amount of the positive active material, namely 100ppm) in a high-speed mixer for 15min, and sintering the powder at a high temperature of 600 ℃ for 10h in a high-temperature oxygen atmosphere furnace to obtain the coating thickness<2nm LiNi0.83Co0.12Mn0.05O2。
The positive electrode active materials prepared in examples 1 to 5 and comparative examples 1 to 2 were respectively subjected to lithium ion battery fabrication, and the cycle performance thereof was tested, and the lithium ion battery fabrication method was as follows:
mixing an artificial graphite negative electrode active material, styrene diene rubber (SBR), sodium carboxymethylcellulose and conductive carbon black in a weight ratio of 94% to 3% to 2% to 1%, dispersing the mixture in water, and mixing by double planets to obtain negative electrode slurry. And coating the slurry on a copper current collector, and then rolling and drying to obtain the negative pole piece.
The positive electrode active materials prepared in examples 1 to 5 and comparative examples 1 to 2 were mixed with conductive carbon and PVDF binder in a weight ratio of 96%: 2%: 2%, and dispersed to obtain positive electrode slurry. Coating the slurry on an aluminum foil current collector, rolling to prepare a positive pole piece, assembling the positive pole piece, a negative pole piece and a diaphragm into a lithium ion battery, and injecting a non-aqueous electrolyte.
Among them, the nonaqueous electrolytic solution used is a conventional electrolytic solution known in the art, and the solvent contains ethylene carbonate (abbreviated as EC), diethyl carbonate (abbreviated as DEC), propylene carbonate (abbreviated as PC), fluoroethylene carbonate (abbreviated as FEC), and the like. The membranes used are commercially available membranes known in the art. And (3) carrying out cycle performance test on the assembled lithium ion battery, wherein the test process is as follows:
charging to 4.2V at a constant current at a charging rate of 1C at 45 ℃, then charging to 0.05C at a constant voltage at 4.2V and cutting off, then discharging to 3.0V at a discharging rate of 1C, repeating 1000 times of the charging and discharging cycles, measuring the discharging capacity at the first cycle and the discharging capacity at the 1000 th cycle, and calculating the capacity retention rate after the cycle, wherein the calculation formula is as follows:
capacity retention rate after cycling (discharge capacity at 1000 cycles)/(discharge capacity at first cycle) 100%.
TABLE 1 cyclability of lithium ion batteries prepared in examples and comparative examples
Capacity retention rate of 1000 times of high temperature 45 ℃ cycle
Example 1 86.8％
Example 2 85.9％
Example 3 90.2％
Example 4 81.9％
Example 5 79.1％
Comparative example 1 74.5％
Comparative example 2 80.1％
From the test results of table 1 above:
it can be seen from comparative examples 1 to 2 or comparative examples 4 to 5 that the lithium ion battery assembled with the positive active material prepared by using the relatively low temperature plasma gas as the reaction raw material has better cycle performance than the lithium ion battery prepared with the positive material prepared by using the reaction raw material of the slightly high temperature steam, indicating that the surface coated Al obtained by using the plasma as a reactant2O3The coating structure has the advantages that the uniformity is higher, the ALD atomic deposition coating effect induced by medium-low temperature plasma is more uniform, the ALD atomic deposition of the high-temperature water vapor induced reaction is higher, the positive active material can be prevented from being damaged or side reaction can be avoided, and the improvement of the cycle performance of the battery is facilitated.
As can be seen from comparative examples 1-2 and comparative examples 1-2, although conventional dry coating of Al was employed2O3The powder mode can also improve the electrochemical cycle performance of the positive active material prepared from the high-nickel material, but the coating uniformity is poor, and the electrochemical cycle performance of the high-nickel positive active material obtained by the ALD atomic deposition through high-temperature water vapor induced reaction and the ALD atomic deposition through low-temperature plasma induced reaction is obviously improved.
The positive electrode active materials prepared in examples 1 to 5 and comparative examples 1 to 2 were placed in the air for a self-weight increase experiment, and the test methods were as follows: 20g of positive active material is respectively taken by a beaker, the positive active material is placed in a place with the indoor temperature of 25-27 ℃ and the environmental humidity of 30-35 percent, the weight of the pole piece is tested by using a high-precision fine balance with the precision of 0.01mg every certain time (one day is selected as a time interval in the test), the weight change is recorded, and the test result is shown in table 2.
Table 2 percentage of self-weight increase (%) -of positive electrode active material prepared in examples and comparative examples
0D 1D 2D 3D 4D 5D 6D 7D
Example 1 0.0000％ 0.0760％ 0.1320％ 0.1780％ 0.1890％ 0.2350％ 0.2750％ 0.2980％
Example 2 0.0000％ 0.0830％ 0.1580％ 0.2030％ 0.2490％ 0.2920％ 0.3650％ 0.3830％
Example 3 0.0000％ 0.0380％ 0.0510％ 0.0880％ 0.1290％ 0.1750％ 0.1920％ 0.2190％
Example 4 0.0000％ 0.1670％ 0.3890％ 0.4140％ 0.5170％ 0.6960％ 0.7430％ 0.8260％
Example 5 0.0000％ 0.1900％ 0.4170％ 0.5430％ 0.5810％ 0.7720％ 0.8940％ 1.0100％
Comparative example 1 0.0000％ 0.8250％ 1.2120％ 1.5400％ 1.7320％ 1.8830％ 2.1010％ 2.2930％
Comparative example 2 0.0000％ 0.5900％ 0.9180％ 1.1430％ 1.3880％ 1.5270％ 1.8040％ 1.9310％
Table 2 shows the percentage (%) of self-weight increase of the positive active material in the same 30% humidity environment, which is obtained in the different examples and comparative examples, and from the test results in table 2, we can intuitively find the following rules:
it can be seen from comparative examples 1 to 2 or comparative examples 3 to 4 that the lithium ion battery assembled with the positive electrode active material prepared by using the plasma gas of relatively low temperature as the reaction raw material is slightly less sensitive to moisture and carbon dioxide in the air under the same environment than the lithium ion battery assembled with the positive electrode active material prepared by using the reaction raw material of water vapor of slightly higher temperature, indicating that the surface-coated Al obtained by using the plasma as a reactant2O3More uniform, and the ALD atomic deposition coating effect induced by the medium-low temperature plasma is more uniform than that of the ALD atomic deposition induced by the high-temperature water vapor.
As can be seen from comparison of examples 1 to 5, when the positive electrode active material was coated by the same coating method, the positive electrode active material was increased in weight, mainly because the positive electrode active material was different in the degree of sensitivity to moisture, and the positive electrode active material of examples 4 to 5 had the highest content of nickel and therefore had the highest weight increase ratio.
Comparative examples 1 to 5 and comparative examples 1 to 2 show that Al is coated by a conventional dry method2O3The powder mode can also improve the storage stability of the positive active material prepared from the high-nickel material, but the storage stability is not obviously improved due to poor coating uniformity, and the high-nickel positive active material prepared by ALD atomic deposition through high-temperature water vapor induced reaction and ALD atomic deposition through low-temperature plasma induced reaction has better performanceThe storage stability of the alloy is high, and particularly, the high nickel material coated by ALD atomic deposition of low-temperature plasma-induced ALD atomic deposition coating effect is higher than that of ALD atomic deposition of high-temperature water vapor-induced reaction has higher air corrosion resistance.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The positive electrode active material is characterized in that a coating layer is coated on the surface and/or in pores of the positive electrode active material, the coating layer is an oxide coating layer or a nitride coating layer, and the coating layer is obtained after a first coating material source and a second coating material source react.
2. The positive electrode active material according to claim 1, wherein the coating layer has a thickness of 10nm or less.
3. A method for producing a positive electrode active material according to claim 1 or 2, comprising the steps of:
s1) placing the positive active substance into a reaction chamber of atomic layer deposition equipment filled with inert gas in advance, and preserving heat;
s2) introducing a first coating substance source into a reaction chamber of the atomic layer deposition equipment, wherein the first coating substance source is adsorbed on the pores and the surface of the positive active material; introducing gas which does not react with the first coating substance source into a reaction chamber of the atomic layer deposition equipment;
s3) introducing a second coating substance source into a reaction chamber of the atomic layer deposition equipment, wherein the second coating substance chemically reacts with the first coating substance source adsorbed on the pores and the surface of the positive electrode active substance to form a coating layer; introducing inert gas into a reaction chamber of the atomic layer deposition equipment;
s4) repeating the steps S2) and S3) at least once, to obtain the positive electrode active material having a coating layer on the surface.
4. The production method according to claim 3, wherein, in step S1), the positive electrode active material is selected from a positive electrode active material of nickel cobalt lithium manganate (Li)zNixCoyMn1-x-yO2Wherein z is more than or equal to 0.95 and less than or equal to 1.05, x>0，y>0，x+y<1) Lithium nickel cobalt aluminate-based positive electrode active material (Li)zNixCoyAl1-x-yO2Wherein z is more than or equal to 0.95 and less than or equal to 1.05, x>0，y>0，0.8≤x+y<1) Lithium nickel cobalt manganese aluminate positive electrode active material (Li)zNixCoyMnwAl1-x-y-wO2Wherein, z is more than or equal to 0.95 and less than or equal to 1.05, x>0，y>0，w>0，0.8≤x+y+w<1)。
5. The production method according to claim 3 or 4, wherein the method further comprises the steps of:
s0) heat-treating the positive electrode active material; and/or the presence of a gas in the gas,
in step S0), the temperature of the heat treatment is 60 to 350 ℃.
6. The production method according to any one of claims 3 to 5, wherein in step S1), the temperature in the reaction chamber of the atomic layer deposition apparatus is 60 to 350 ℃; and/or the presence of a gas in the gas,
in step S1), the inert gas is at least one of nitrogen, argon and helium; and/or the presence of a gas in the gas,
in step S2), the first coating material source is an organometallic compound or a metal halide; and/or the presence of a gas in the gas,
the organic metal compound is selected from at least one of trimethyl aluminum, triethyl aluminum, triethoxy aluminum, trimethyl borane, triethyl borane, diborane, titanium triisopropoxide, tetraethoxy titanium, titanium tetraisopropoxide, zirconium tetra-tert-butoxide, trimethyl magnesium, triethyl magnesium, pentaethoxy tantalum, trimethyl zinc or triethyl zinc; the metal halide is selected from at least one of aluminum tribromide, aluminum trichloride, boron tribromide, titanium tetraiodide, titanium tetrachloride, zirconium tetraiodide or tantalum pentachloride; and/or the presence of a gas in the gas,
in step S2), the gas that is not reactive with the first coating substance source is at least one selected from argon, nitrogen, and helium.
7. The production method according to any one of claims 3 to 6, wherein in step S3), the second coating material source is a gas that can react with the first coating material source to form an oxide or nitride, or a material that can react with the first coating material source to form an oxide or nitride and that can be atomized or vaporized by treatment, or a plasma gas that can react with the first coating material source to form an oxide or nitride; and/or the presence of a gas in the gas,
the gas is selected from water (H)2O), ozone (O)3) Oxygen (O)2) (ii) a The substance capable of atomizing or gasifying after treatment is selected from hydrogen peroxide (H)2O2) Methanol (CH)3OH) or ethanol (CH)3CH2OH); the plasma gas is selected from ozone (O)3) Oxygen (O)2) Ammonia (NH)3) Helium (He), hydrogen (H)2) Argon (Ar), neon (Ne), and water (H)2O), Nitric Oxide (NO), tetrafluoromethane (CF)4) Hexafluoroethane (C)2F6) Carbon dioxide (CO)2) (ii) a And/or the presence of a gas in the gas,
in step S3), the inert gas is selected from nitrogen or argon.
8. The production method according to any one of claims 3 to 7, wherein a pressure of a reaction chamber of the atomic layer deposition apparatus is 1Pa to 2 kPa.
9. A positive electrode sheet comprising the positive electrode active material according to claim 1 or 2 or produced by the production method according to any one of claims 3 to 8.
10. A lithium ion battery comprising the positive electrode active material according to claim 1 or 2, or comprising the positive electrode sheet according to claim 9.
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Application publication date: 20210319