CN110690445B - Preparation method of polyaluminium coated nickel cobalt lithium manganate material - Google Patents

Preparation method of polyaluminium coated nickel cobalt lithium manganate material Download PDF

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CN110690445B
CN110690445B CN201910970074.0A CN201910970074A CN110690445B CN 110690445 B CN110690445 B CN 110690445B CN 201910970074 A CN201910970074 A CN 201910970074A CN 110690445 B CN110690445 B CN 110690445B
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nickel cobalt
temperature
lithium manganate
manganate material
polyaluminium
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CN110690445A (en
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童庆松
张晓红
祖国晶
席强
王彤
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Fujian Normal University
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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
    • H01M4/48—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
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a preparation method of a nickel cobalt lithium manganate material coated with polyaluminium, which is characterized in that the polyaluminium is mixed with the nickel cobalt lithium manganate material, ammonia water is added to prepare a precursor, and the precursor is dried to prepare layered alpha-NaFeO by adopting a programmed heating method or a temperature-region-by-temperature heating method2The nickel cobalt lithium manganate material with the structure and coated with the polymeric aluminum. Nickel of the lithium nickel cobalt manganese oxide material: cobalt: molar ratio of manganese ions: (0.47-0.52), (0.15-0.25), (0.25-0.35), (0.57-0.62), (0.15-0.25), (0.77-0.82), (0.05-0.15). The sample prepared by the invention has obviously improved high-current discharge and storage performance.

Description

Preparation method of polyaluminium coated nickel cobalt lithium manganate material
Technical Field
The invention belongs to the technical field of battery electrode material preparation, and relates to a preparation method of a nickel cobalt lithium manganate material for lithium batteries, lithium ion batteries, polymer batteries and supercapacitors.
Technical Field
The lithium ion battery has the advantages of high voltage, light weight, long cycle life, no memory effect, good safety and the like, and can be widely applied to digital products such as mobile phones, digital cameras, notebook computers and the like and power tools such as electric vehicles, hybrid electric vehicles and the like. The lithium ion battery comprises a positive electrode material, a negative electrode material, a diaphragm, electrolyte, a current collector and the like. The positive electrode material is a key for restricting the overall performance and cost of the lithium ion battery. Lithium manganate, lithium iron phosphate, lithium cobaltate, etc. are commercially available as positive electrode materials. In 1997, Ohzuku and Makimura [ Ohzuku T, Makimura Y., chem. Let., 2001, (7): 642-643.]LiNi was first reported1/3Mn1/3Co1/3O2The layered nickel cobalt lithium manganate material.Then the composition is LiNi0.5Co0.2Mn0.3O2、LiNi0.4Co0.2Mn0.4O2The nickel cobalt lithium manganate material is also invented. This material LiNixCoyMnzO2Has both LiCoO and LiCoO2、LiNiO2And LiMnO2Has obvious synergistic effect. The stoichiometric ratio and distribution of the elements of the material are key factors affecting the performance. The method for synthesizing the nickel cobalt lithium manganate material comprises a high-temperature solid phase method, a coprecipitation method, a spray drying method, a hydrothermal method, a sol-gel method and the like. Wherein, the coprecipitation method is a main method for preparing the nickel cobalt lithium manganate material.
The coprecipitation method is to add a precipitator and a complexing agent into a mixed solution of various cations to control the nucleation and growth processes of precipitation, so as to obtain coprecipitation with controllable morphology and particle size. And filtering and drying the prepared coprecipitation to obtain a precursor. The precursor is mixed with lithium salt and then prepared into the anode material by a high-temperature sintering method. The synthesis method has good reproducibility, and the prepared product has uniform composition. The morphology and the particle size of a coprecipitation product can be controlled by controlling the stirring speed, the pH value, the aging temperature, the precipitating agent, the dropping speed of the precipitating agent, the proportion of ammonia water and metal ions and the like in the precipitation process, and the problems of uneven material mixing, too wide particle size distribution and the like in the solid-phase synthesis method are solved. The coprecipitation method is classified into a hydroxide and carbonate coprecipitation method. Specifically, a hydroxide or carbonate precipitator is used for forming precursor precipitates of transition metal ions, then the precursor precipitates are mixed with lithium salt, and finally the lithium nickel cobalt manganese oxide material is prepared by sintering. The hydroxide coprecipitation method is a common method for synthesizing a precursor of the nickel cobalt lithium manganate material. The method generally uses NaOH as a precipitator and ammonia water as a complexing agent, uses the precipitator to control the pH value in the reaction process, and realizes the purpose of controlling the particle size and the morphology of a precursor by controlling the reaction temperature and the stirring speed, thereby finally optimizing the electrochemical performance of the nickel cobalt lithium manganate material. During the preparation, due to the intermediate product Mn (OH) formed2The precursor is unstable and is easily oxidized by air, and the performance of the material is affected, so nitrogen needs to be introduced for protection in the process of preparing the precursor. Hydroxide coprecipitationThe method has the advantages that the precursor with uniform particle size can be controlled; the disadvantage is the complex preparation process. The coprecipitation method is classified into a hydroxide and carbonate coprecipitation method.
The lithium nickel cobalt manganese oxide material can be expressed as LiNixCoyMnzO2(wherein x + y + z = 1). According to different mole ratios of nickel, cobalt and manganese elements in the chemical formula, the nickel cobalt lithium manganate material can be divided into different types. For example, the Ni-Co-Mn acid material with the mol ratio of Ni, Co and Mn (x: y: z) of 3: 3 is called 333 type for short; the nickel cobalt lithium manganate material with the mole ratio of nickel, cobalt and manganese of 5: 2: 3 is called 523 type; the nickel cobalt lithium manganate material with the molar ratio of nickel, cobalt and manganese of 8: 1 is called 811 type, and other similar types are available. The 333 type, 523 type, 622 type and 811 type nickel cobalt lithium manganate materials all have alpha-NaFeO2And a layer-shaped structure. In the nickel cobalt lithium manganate material, the valences of nickel, cobalt and manganese elements are respectively +2 valences, +3 valences and +4 valences. Ni is the main active element. Theoretically, the higher the relative content of nickel, the higher the discharge capacity of the lithium nickel cobalt manganese oxide material.
The nickel cobalt lithium manganate material with better thermal stability and cycling stability is the premise for realizing the application. The nickel cobalt lithium manganate material prepared at present has the following problems: poor cycle performance, poor compatibility with electrolyte, and safety in use. The purpose of increasing the discharge capacity of the nickel cobalt lithium manganate material can be realized by increasing the charge cut-off voltage. However, under a high charge cut-off voltage, the side reaction between the cathode material and the electrolyte is obviously intensified, and the cycle stability of the cathode material is damaged. When charging and discharging are carried out at higher working temperature or under high-rate current, the thermal stability and the cycling stability of the nickel cobalt lithium manganate material are also reduced. When charging and discharging are carried out at low temperature, the conductivity of the nickel cobalt lithium manganate material can be obviously reduced, the impedance is increased, and the discharge performance of the anode is influenced. Therefore, the nickel cobalt lithium manganate material prepared at present is modified by the following method. Including doping, surface coating, surface treatment, and the like. The coating can improve the electronic conductivity and the ionic conductivity of the nickel cobalt lithium manganate material, and obviously improve the cycle stability and the thermal stability of the nickel cobalt lithium manganate material. Coatings that have been investigated include metal oxides, metal fluorides [ Shi S J, et al, J. Power Sources, 2013, 225: 338-; yang K, et al, Electrochim. Acta, 2012, 63: 363-.
Because the nickel cobalt lithium manganate material has lower electronic conductivity, the nickel cobalt lithium manganate material coated by carbon or polymer with better conductivity can improve the electronic conductivity and improve the electrochemical performance. Xiong et al [ Xiong X, et al, J. Solid State electrochem, 2014, 18 (9): 2619-2624 ] use polymerization to prepare polypyrrole-coated 811 type nickel cobalt lithium manganate material, improve the cycling stability of samples at high temperature and high charge cut-off voltage, and also improve the rate discharge performance of the material. Mei et al [ Mei T, et al, Rsc Advances, 2012, 2(33): 12886-12891 ]) takes PEG (600) as a dispersing agent and a carbon source, and coats PEG on the surface of 333 type nickel cobalt lithium manganate material, so that the cycling stability of the material under high charge cut-off voltage is improved (the 100-cycle capacity fading rate is less than 3% in a voltage range of 2.8-4.6V and under 1C rate current).
For coatings of metal oxides [ Yano a, et al, j. electrochem. soc., 2015, 162(2): a3137-a 3144; kong J Z, et al, J, Alloys and Compounds, 2013, 554: 221-.]In other words, Al2O3Has poor conductivity but good chemical stability. With Al2O3The nickel cobalt lithium manganate material is coated, so that the side reaction of the electrolyte and the nickel cobalt lithium manganate material can be slowed down, and the circulation stability is improved. Preparation of Al by the sol-gel method2O3And (3) coating 333 type nickel cobalt lithium manganate material. Al (Al)2O3The coating significantly improved the cycling stability of the samples at high charge cut-off voltage. The research shows that the charge cut-off voltage is respectively 4.5V, 4.6V and 4.7V, and Al is2O3The capacity retention rates of the coated 333 type nickel cobalt lithium manganate material at 100 cycles are respectively 98%, 90% and 71%; the capacity retention rates of the uncoated lithium nickel cobalt manganese oxide material under corresponding charge cut-off voltages are respectively 25%, 16% and 32%. The study shows that Al2O3The coating inhibits the side reaction between the nickel cobalt lithium manganate material and the electrolyte.
Although a great deal of research on the lithium nickel cobalt manganese oxide material is carried out by changing the synthesis method, coating, doping modification and other means, the lithium nickel cobalt manganese oxide material still has the problems of low discharge capacity, hidden danger in safety, improvement of cycle performance and the like.
Polyaluminium (polyaluminium chloride, formula which may be written as [ Al ]2(OH) nCl6-n]mWherein n is 1 to 5, and m is an integer of not more than 10) is a cationic inorganic polyelectrolyte. The molecular weight of the polymeric aluminum is lower than that of the organic polymer and higher than that of the general complex. The polymeric aluminum inorganic polyelectrolyte has positive charges and is composed of polymers of aluminum with different polymerization degrees and even different structural forms. The presence of different polymeric aluminum depends on manufacturing and storage conditions. Among the various forms of polymeric aluminum, Al13 ( [AlO4Al12(OH)24(H2O)l2]7+ ) Morphology is of great interest [ Xu Y, et a1., Colloid surf. a-physiochem. eng. asp., 2003.231: l-9, Wang S. L., et a1., Colloid surf. A-Physicochem. Eng. Asp., 2003, 231: 43-l57, Gao B. Y., et a1., J. environ. manage, 2005, 76: l43-l47]. Prefabricated Al, in addition to high positive charge and strong bridging capacity13The polymer is stable in the coagulation process. Al is considered by many scholars13Morphology is the most effective component of polyaluminium in coagulation [ buffer j., et a1., wat. res., 1985, l 9: 7-23, Tang H. X., et a1., J. environ.Sci., 1995, 7: 2O4-211]Thus, All3Polymers have been targeted for use in polymeric aluminum manufacturing processes [ passrtharathy n., et a1., wat. res., 1985, 19: 25-36]. Compared with other aluminum salts or iron salts, the polymeric aluminum has a series of advantages of small dosage, strong adaptability, quick flocculation formation and the like.
The action mechanism of the polyaluminium chloride in the coagulation process has the characteristics. The coagulation action mechanism of the polyaluminium comprises three aspects: firstly, the coagulation effect of electric neutralization and destabilization of colloid particles; secondly, the flocculation of adsorption bridging is carried out to the secondary coarse particles which are condensed: and thirdly, removing harmful ions in water by adsorption and complexation. The degree of alkalization affects the degree of polymerization and the amount of charge of the polyaluminum high polymer compared to aluminum sulfate. The performance of the polymeric aluminum can be controlled by effectively controlling the polymerization reaction of the polymeric aluminum. Compared with aluminum sulfate, the polyaluminum chloride has the advantages of wide range of the best use value p H, high floc forming speed, good precipitation performance, small addition amount and the like. [ Zhao Li, Master academic paper of Hefei industrial university, 2012.4 ].
Disclosure of Invention
In order to improve the defects of the lithium nickel cobalt manganese oxide material, the invention adopts a method of coating polymeric aluminum to improve the performance of the lithium nickel cobalt manganese oxide material. In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
diluting the polyaluminum solution into solution [ AlO ] with water4Al12(OH)24(H2O)l2]7+The concentration is in the range of 0.00001-0.1 mmol/L to obtain the diluted solution. According to the volume ratio of 1: (0.1-1000) mixing the nickel cobalt lithium manganate material with the diluent to prepare a mixed solution 1. Under the condition of continuous stirring, ammonia water is dripped until the acidity of the mixed solution 1 is within the range of pH 9.5-13.0, and the mixed solution is aged for 3-48 hours at any temperature within the temperature range of 65-95 ℃ to prepare a precursor 1. Drying the precursor 1 at any temperature in the range of 160-280 ℃ in vacuum to prepare a dried precursor 2; or spray drying at any temperature in the range of 160-280 ℃ to prepare the dried precursor 2. The dried precursor 2 is put into oxygen-enriched air or pure oxygen atmosphere, and the layered alpha-NaFeO is prepared by adopting a programmed heating method or a temperature-region-by-temperature-region heating method2The nickel cobalt lithium manganate material with the structure and coated with the polymeric aluminum.
The nickel cobalt lithium manganate material simultaneously meets the following characteristics that diffraction peaks on an XRD diffraction pattern and layered alpha-NaFeO2The characteristic diffraction peaks of the structures (JCPDS card 09-0063) were matched. The button half-cell prepared has the charge specific capacity ratio of less than 25% increased compared with the charge to 4.4V when the button half-cell is charged to 4.6V in a constant current relative to the lithium electrode under the conditions of 0.2C rate current and the 1 st charge-discharge cycle. Is different from the lithium-rich manganese-based solid solution material. The XRD diffraction pattern of the sample has no pairs in the range of 20-25 degrees of 2 theta angleShould be Li2MnO3Diffraction peaks of (JCPDS cards 27-1252).
The nickel content of the nickel cobalt lithium manganate material is as follows: cobalt: molar ratio of manganese ion x: y: z simultaneously satisfies the following conditions: (0.47-0.52), (0.15-0.25), (0.25-0.35), (0.57-0.62), (0.15-0.25), (0.77-0.82), (0.05-0.15), and x + y + z = 1.
The programmed heating method is carried out by placing the dried precursor 2 in oxygen-enriched air or pure oxygen atmosphere, carrying out programmed heating from room temperature to any temperature within the temperature range of 300-650 ℃ according to the heating speed of 0.2-50 ℃/min, sintering for 3-24 hours at any temperature, and cooling to room temperature to obtain the layered alpha-NaFeO2The nickel cobalt lithium manganate material coated with the polyaluminium is structurally.
The temperature-region-by-temperature-region heating method is carried out by placing the dried precursor 2 in oxygen-enriched air or pure oxygen atmosphere, heating to any temperature within the temperature range of 300-650 ℃ from the room temperature region according to the heating speed of 0.2-50 ℃/temperature region, and cooling to room temperature to obtain the layered alpha-NaFeO2The nickel cobalt lithium manganate material coated with the polyaluminium is structurally.
The liquid medium is deionized water, distilled water, ethanol, acetone, methanol or propanol.
The oxygen-enriched air is air with the oxygen volume content of 30-99%.
The mixing equipment is ball milling or sanding equipment.
The invention has the advantages of low cost of raw materials, wide raw material sources, simple preparation process, simple and convenient operation and less time consumption. The sewage discharged in the preparation process is obviously reduced, and LiMn does not exist in the prepared sample6A superlattice structure. The ratio of the increased specific charge capacity of the material when charged to 4.6V at constant current to the positive electrode of the lithium electrode compared with 4.4V is less than 25%. Is different from the lithium-rich manganese-based solid solution material. The prepared electrode material has good consistency, uniform composition, excellent discharge performance and cycle performance, and good discharge cycle performance under the condition of large current, and lays a good foundation for industrialization.
Detailed Description
The present invention will be further described with reference to the following examples. The examples are merely further additions and illustrations of the present invention, and are not intended to limit the invention.
Example 1
Diluting the polyaluminum solution into solution [ AlO ] with water4Al12(OH)24(H2O)l2]7+The concentration was 0.01 mmol/L, and a diluted solution was obtained. According to the volume ratio of 1: and 15, uniformly mixing the nickel cobalt lithium manganate material with the diluent to prepare a mixed solution 1. Ammonia water was added dropwise with continuous stirring until the acidity of the solution was pH 12. Aging at 70 ℃ for 30 hours to obtain a mixture as precursor 1. And drying the precursor 1 at 200 ℃ in vacuum to obtain a dried precursor 2. The precursor 2 is put into oxygen-enriched air with the oxygen volume content of 75 percent, heated from room temperature to 550 ℃ at the speed of 5 ℃/min, sintered for 12 hours at 550 ℃, and cooled to room temperature to prepare the layered alpha-NaFeO2The nickel cobalt lithium manganate material coated with the polyaluminium is structurally. The nickel-cobalt lithium manganate material comprises nickel: cobalt: the molar ratio of manganese ions was 0.5: 0.20: 0.30.
The nickel cobalt lithium manganate material simultaneously meets the following characteristics that diffraction peaks on an XRD diffraction pattern and layered alpha-NaFeO2The characteristic diffraction peaks (JCPDS card 09-0063) of the structure are matched, and the ratio of the charging specific capacity increased when the button-type half cell prepared from the nickel cobalt lithium manganate material is charged to 4.6V relative to the constant current of a lithium electrode under the conditions of 0.2C rate current and 1 st cycle charging and discharging is 11 percent; the XRD diffraction pattern of the sample has no weak diffraction peak in the range of 20-25 degrees of 2 theta angle and does not correspond to Li2MnO3Diffraction peaks (JCPDS cards 27-1252) were generated by diffraction.
Example 2
Diluting the polyaluminum solution into solution [ AlO ] with water4Al12(OH)24(H2O)l2]7+The concentration was 0.1 mmol/L, and a diluted solution was obtained. According to the volume ratio of 1: and (5) uniformly mixing the nickel cobalt lithium manganate material with the diluent to prepare a mixed solution 1. Under the condition of continuous stirring, ammonia water is dripped until the acidity of the solution is pH 13.0, and the solution is aged for 48 hours at 65 ℃, and the prepared mixture is a precursor 1. To make a precursorThe product 1 was heated at 280 ℃ to obtain a dried precursor 2. The dried precursor 2 is put into pure oxygen atmosphere, is heated to 650 ℃ from room temperature according to the program of 0.2 ℃/min, is sintered for 24 hours at 650 ℃, and is cooled to room temperature to prepare the layered alpha-NaFeO2The nickel cobalt lithium manganate material with the structure and coated with the polymeric aluminum. The nickel content of the nickel cobalt lithium manganate material is as follows: cobalt: the molar ratio of manganese ions was 0.52:0.25: 0.25.
The nickel cobalt lithium manganate material simultaneously meets the following characteristics that diffraction peaks on an XRD diffraction pattern and layered alpha-NaFeO2The characteristic diffraction peaks of the structure (JCPDS card 09-0063) are matched. Under the conditions of 0.2C rate current and 1 st cycle charge and discharge, the ratio of the charge specific capacity of the button type half cell prepared from the nickel cobalt lithium manganate material is increased by 15% compared with the ratio of the charge specific capacity of the button type half cell which is charged to 4.4V by constant current relative to a lithium electrode. The XRD diffraction pattern of the sample has no weak diffraction peak in the range of 20-25 degrees of 2 theta angle and does not correspond to Li2MnO3Diffraction peaks (JCPDS cards 27-1252) were generated by diffraction.
Example 3
Diluting the polyaluminum solution into solution [ AlO ] with water4Al12(OH)24(H2O)l2]7+The concentration was 0.00001 mmol/L to obtain a diluted solution. According to the volume ratio of 1: 0.10 of the lithium nickel cobalt manganese oxide material and the diluent are uniformly mixed to prepare a mixed solution 1. Under the condition of continuous stirring, ammonia water is dripped until the acidity of the solution is pH 9.5, and the solution is aged for 3 hours at 65 ℃, and the prepared mixture is a precursor 1. The precursor 1 is dried in vacuum at 260 ℃ to prepare a dried precursor 2. The dried precursor 2 is put into oxygen-enriched air atmosphere with the oxygen volume content of 99 percent, the room temperature is heated to 450 ℃ according to the program of 50 ℃/min, the sintering is carried out for 24 hours at 450 ℃, and the room temperature is cooled, thus obtaining the lamellar alpha-NaFeO2The nickel cobalt lithium manganate material coated with the polyaluminium is structurally. The nickel-cobalt lithium manganate material comprises nickel: cobalt: the molar ratio of manganese ions was 0.47:0.18: 0.35.
The nickel cobalt lithium manganate material simultaneously meets the following characteristics that diffraction peaks on an XRD diffraction pattern and layered alpha-NaFeO2The characteristic diffraction peaks of the structure (JCPDS card 09-0063) are matched. Preparation of lithium nickel cobalt manganese oxide materialUnder the conditions of 0.2C multiplying current and 1 st cycle charging and discharging, the ratio of the increase of the charging specific capacity to the constant current charging of 4.6V of the prepared button-type half battery relative to the constant current charging of the lithium electrode to 4.4V is 19%. The XRD diffraction pattern of the sample has no weak diffraction peak in the range of 20-25 degrees of 2 theta angle and does not correspond to Li2MnO3Diffraction peaks (JCPDS cards 27-1252) were generated by diffraction.
Example 4
Diluting the polyaluminum solution into solution [ AlO ] with water4Al12(OH)24(H2O)l2]7+The concentration was 0.001 mmol/L, and a diluted solution was obtained. According to the volume ratio of 1: 100, uniformly mixing the nickel cobalt lithium manganate material with the diluent to prepare a mixed solution 1. Under the condition of continuous stirring, ammonia water is dripped until the acidity of the solution is pH 13.0, and the solution is aged for 48 hours at 95 ℃, and the prepared mixture is a precursor 1. And drying the precursor 1 at 160 ℃ in vacuum to obtain a dried precursor 2. The precursor 2 is put into pure oxygen atmosphere, is heated to 300 ℃ from room temperature by a program at the speed of 0.2 ℃/min, is sintered for 3 hours at 300 ℃, and is cooled to room temperature to prepare the lamellar alpha-NaFeO2The nickel cobalt lithium manganate material with the structure and coated with the polymeric aluminum. The lithium nickel cobalt manganese oxide material is characterized in that the weight ratio of nickel: cobalt: the molar ratio of manganese ions was 0.52: 0.15: 0.33.
The nickel cobalt lithium manganate material simultaneously meets the following characteristics that diffraction peaks on an XRD diffraction pattern and layered alpha-NaFeO2The characteristic diffraction peaks of the structure (JCPDS card 09-0063) are matched. Under the conditions of 0.2C rate current and 1 st cycle charge and discharge, the ratio of the increased specific charge capacity of the button-type half battery prepared from the nickel cobalt lithium manganate material when the button-type half battery is charged to 4.6V in comparison with the constant current of a lithium electrode is 16 percent. The XRD diffraction pattern of the sample does not have weak diffraction peaks in the range of 20-25 degrees of 2 theta angle and does not correspond to Li2MnO3Diffraction peaks (JCPDS cards 27-1252) were generated by diffraction.
Example 5
Diluting the polyaluminum solution into solution [ AlO ] with water4Al12(OH)24(H2O)l2]7+The concentration was 0.02 mmol/L, and a diluted solution was obtained. According to the volume ratio of 1: 1000 evenly mixing the lithium nickel cobalt manganese oxide material with the diluentTo prepare a mixed solution 1. Under the condition of continuous stirring, ammonia water is dripped until the acidity of the solution is pH 11.0, and the solution is aged for 3 hours at 65 ℃, and the prepared mixture is a precursor 1. The precursor 1 was dried under vacuum at 230 c to produce dried precursor 2. The precursor 2 is placed in a pure oxygen atmosphere, the room temperature is heated to 420 ℃ from the room temperature by a program at the speed of 0.8 ℃/min, the sintering is carried out for 24 hours at the temperature of 420 ℃, and the room temperature is cooled to obtain the lamellar alpha-NaFeO2The structure is a nickel cobalt lithium manganate material coated with polymeric aluminum. The nickel-cobalt lithium manganate material comprises nickel: cobalt: the molar ratio of manganese ions was 0.57: 0.25: 0.15.
The nickel cobalt lithium manganate material simultaneously meets the following characteristics that diffraction peaks on an XRD diffraction pattern and layered alpha-NaFeO2The characteristic diffraction peaks of the structure (JCPDS card 09-0063) are matched. Under the conditions of 0.2C rate current and 1 st cycle charge and discharge, the ratio of the charge specific capacity of the button-type half battery prepared from the nickel cobalt lithium manganate material is increased by 19% compared with the ratio of the charge specific capacity of the button-type half battery prepared from the nickel cobalt lithium manganate material when the button-type half battery is charged to 4.6V by constant current relative to a lithium electrode and is charged to 4.4V. The XRD diffraction pattern of the sample does not have weak diffraction peaks in the range of 20-25 degrees of 2 theta angle and does not correspond to Li2MnO3Diffraction peaks (JCPDS cards 27-1252) were generated by diffraction.
Example 6
Diluting the polyaluminum solution into solution [ AlO ] with water4Al12(OH)24(H2O)l2]7+The concentration was 0.03 mmol/L, and a diluted solution was obtained. According to the volume ratio of 1: 1, uniformly mixing the nickel cobalt lithium manganate material with the diluent to prepare a mixed solution 1. Under the condition of continuous stirring, ammonia water is dripped until the acidity of the solution is pH 9.5, and the solution is aged for 48 hours at 75 ℃, and the prepared mixture is a precursor 1. Precursor 1 was spray dried at 200 ℃ to prepare dried precursor 2. The precursor 2 is placed in pure oxygen atmosphere, is gradually heated from a room temperature region to 300 ℃ at a heating speed of 50 ℃/temperature region, and is cooled to room temperature to prepare the layered alpha-NaFeO2The nickel cobalt lithium manganate material with the structure and coated with the polymeric aluminum. The nickel-cobalt lithium manganate material comprises nickel: cobalt: the molar ratio of manganese ions was 0.57:0.18: 0.25.
The nickel cobalt lithium manganate material simultaneously meets the following characteristics that diffraction peaks on an XRD diffraction pattern and layered alpha-NaFeO2The characteristic diffraction peaks of the structure (JCPDS card 09-0063) are matched. Under the conditions of 0.2C rate current and 1 st cycle charge and discharge, the proportion of increasing the specific charge capacity by 21 percent compared with the constant current charge to 4.6V and the constant current charge to 4.4V of a lithium electrode is increased. No weak diffraction peak appears in the range of 20-25 degrees of 2 theta angle of XRD diffraction pattern of the sample, and no weak diffraction peak corresponds to Li2MnO3Diffraction peaks (JCPDS cards 27-1252) were generated by diffraction.

Claims (6)

1. The preparation method of the nickel cobalt lithium manganate material coated with the polyaluminium is characterized by comprising the following preparation steps: diluting the polyaluminum solution into solution [ AlO ] with water4Al12(OH)24(H2O)l2]7+The concentration is in the range of 0.00001-0.1 mmol/L to obtain a diluent; according to the volume ratio of 1: (0.1-1000) mixing the nickel cobalt lithium manganate material with a diluent to prepare a mixed solution 1; under the condition of continuous stirring, dropwise adding ammonia water until the acidity of the mixed solution 1 is within the range of pH 9.5-13.0, and aging at any temperature within the temperature range of 65-95 ℃ for 3-48 hours to prepare a precursor 1; drying the precursor 1 at any temperature within the range of 160-280 ℃ in vacuum to prepare a dried precursor 2; or spray drying the precursor 1 at any temperature within the range of 160-280 ℃ to prepare a dried precursor 2; the dried precursor 2 is put into oxygen-enriched air or pure oxygen atmosphere, and the layered alpha-NaFeO is prepared by adopting a programmed heating method or a temperature-region-by-temperature-region heating method2A nickel cobalt lithium manganate material with a structure and coated with polyaluminium;
the nickel cobalt lithium manganate material coated with the polyaluminium simultaneously meets the following characteristics that diffraction peaks on an XRD diffraction pattern and layered alpha-NaFeO2The diffraction peak JCPDS card 09-0063 of the structural feature is coincided; the ratio of the increased specific charge capacity of the button half cell relative to the constant current charging of a lithium electrode to 4.6V to 4.4V is less than 25 percent under the conditions of 0.2C multiplying current and the 1 st charge-discharge cycle; the XRD diffraction pattern of the nickel cobalt lithium manganate material coated with the polyaluminium is free from corresponding Li in the range of 20-25 degrees of 2 theta angle2MnO3Diffraction peaks of JCPDS cards 27-1252;
the lithium nickel cobalt manganese oxide material is shown in the specificationShown as LiNixCoyMnzO2The molar ratio of nickel, cobalt and manganese ions simultaneously satisfies the following conditions: y is z is (0.47-0.52), (0.15-0.25), (0.25-0.35) or (0.57-0.62), (0.15-0.25) or (0.77-0.82), (0.05-0.15), and x + y + z = 1.
2. The method for preparing the polyaluminum coated lithium nickel cobalt manganese oxide material according to claim 1, wherein the programmed heating method is carried out by placing the dried precursor 2 in an oxygen-enriched air or pure oxygen atmosphere, programmed heating from room temperature to any temperature in the range of 300-650 ℃ at a heating rate of 0.2-50 ℃/min, sintering at any temperature for 3-24 hours, and cooling to room temperature to obtain the layered alpha-NaFeO2The nickel cobalt lithium manganate material coated with the polyaluminium is structurally.
3. The method for preparing the lithium nickel cobalt manganese oxide material coated with the polyaluminum silicate according to claim 1, wherein the temperature-region-by-temperature-region heating method is carried out by placing the dried precursor 2 in an oxygen-enriched air or pure oxygen atmosphere, heating from a room temperature region to any temperature in a temperature range of 300-650 ℃ at a heating rate of 0.2-50 ℃/temperature region, and cooling to room temperature to obtain the layered alpha-NaFeO2The nickel cobalt lithium manganate material coated with the polyaluminium is structurally.
4. The method of claim 1, wherein the liquid medium is deionized water, distilled water, ethanol, acetone, methanol or propanol.
5. The method for preparing the poly aluminum coated lithium nickel cobalt manganese oxide material according to claim 1, wherein the oxygen-enriched air is air with an oxygen volume content of 30-99%.
6. The method for preparing the lithium nickel cobalt manganese oxide material coated with the polyaluminium chloride according to claim 1, wherein the mixing equipment is ball milling or sanding equipment.
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