CN117410476A - Preparation method of lithium ion battery anode material - Google Patents

Preparation method of lithium ion battery anode material Download PDF

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Publication number
CN117410476A
CN117410476A CN202311647627.1A CN202311647627A CN117410476A CN 117410476 A CN117410476 A CN 117410476A CN 202311647627 A CN202311647627 A CN 202311647627A CN 117410476 A CN117410476 A CN 117410476A
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lithium ion
positive electrode
fatty acid
coating
electrode material
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李岩
高晗
葛乐
刘铱焓
高宇心
陈乐�
叶余凯
杨宁
阳建中
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Shenzhen Aorui New Energy Technology Co ltd
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Shenzhen Aorui New Energy Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
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    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
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    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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
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    • Y02E60/10—Energy storage using batteries

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Abstract

A method for preparing a lithium ion battery anode material is characterized in that a metal salt of fatty acid is adopted to be mixed with the anode material for the lithium ion battery, and the coated anode material is prepared through high-temperature solid-phase reaction sintering. The preparation method provided by the invention can rapidly realize uniform coating of the positive electrode material and enhance the interface stability of the positive electrode material of the lithium ion battery, thereby enhancing the safety stability and the cycle life of the material and simultaneously obviously improving the resistance rise condition of the battery material after use.

Description

Preparation method of lithium ion battery anode material
The application is a divisional application which is proposed by the original application with the name of a method for preparing a positive electrode material of a lithium ion battery according to the application number of 20201318208. X and 11/20/2020.
Technical Field
The invention relates to a preparation method of an electrode material, in particular to a preparation method of a lithium battery anode material, which further improves various performances of a battery.
Background
The lithium ion battery is used as an energy storage technology with environmental protection, high energy density and good cycle life, and is widely applied to various energy storage devices. In particular, recently, electric vehicles, which have been strongly developed to alleviate environmental pollution, have been widely commercialized for the lithium ion battery industry. The lithium ion battery with excellent performance and low cost is in need of continuous innovation of advanced production technology in large-scale commercial production. Especially, the innovation of the production process of the lithium ion battery material can greatly improve the performance of the whole lithium ion battery and reduce the production cost. As an indispensable component of lithium ion batteries, the production process and cost of the cathode material are always important factors limiting the performance and price of the lithium ion batteries. The industry is continuously pursuing high energy density of lithium ion batteries, and the cycle cut-off voltage of the positive electrode material is forced to be higher and higher. A higher cycle cut-off voltage will cause a greater stress on the interfacial stability of the positive electrode material. How to realize the interface stability of the positive electrode material plays an important role in realizing the stability of the positive electrode material under high cut-off voltage. The current widely adopted technical means is to directly modify the surface of the positive electrode material, and usually, non-electrochemical active materials such as oxide, fluoride and the like are used for directly modifying or coating the surface of the positive electrode material. The oxide, fluoride and other substances coated on the surface of the positive electrode material are utilized to avoid direct contact between the surface of the positive electrode material and electrolyte, so that the surface reactivity of the positive electrode material is reduced, the dissolution of metal ions is reduced, the surface structure transformation of the positive electrode material is delayed, and the like. The whole cycle life and the safety performance of the battery can be improved by coating the anode material.
The anode material is coated by a gas phase method, a liquid phase method and a solid phase method, wherein the solid phase method has the lowest production cost and is most suitable for mass production. However, the solid phase method often causes poor coating effect of the material due to uneven dispersion of the coating in the pretreatment. How to achieve uniform coating of the cathode material by a solid phase method has been a difficulty in the industry.
CN108172826a discloses a method for coating a high nickel ternary material. According to the technology, firstly, low-speed mechanical mixing is carried out on the coating material lithium iron phosphate nano particles and the high-nickel ternary material, and then high-speed mechanical mixing is carried out, so that fusion coating is carried out on the coating material lithium iron phosphate and the high-nickel ternary material, and a coating experiment is completed. The solid phase coating method provided by the technology has high requirements on production equipment, and is difficult to produce in a large scale.
CN108767221a discloses a method for coating a positive electrode material of a lithium ion battery. The technology prepares the anode material coated by the aluminum-titanium alloy by ball milling titanium-aluminum mixed oxide and the anode material and then sintering at high temperature. Also, the technology has complicated production steps and too high equipment requirements, and is unfavorable for mass production.
CN111554907a discloses an application of fatty acid in preparing lithium ion battery and a method for preparing electrode material, the technology uses fatty acid as dispersing agent, firstly mixes fatty acid with coating substance as coating precursor, then mixes the coating precursor with electrode material to perform solid phase sintering, and after high temperature sintering, the fatty acid becomes liquid state to facilitate the coating substance to be dispersed on the surface of electrode material, thus forming uniform coated electrode material. The technology well solves the problem of mass production of the solid state method coating, but still needs to add a little as follows: more than 1% of coating materials such as metal oxides and metal fluorides, and it is desirable to reduce the amount of these coating materials used in the materials for lithium ion batteries, thereby further improving the battery performance.
Disclosure of Invention
The invention aims to provide a preparation method of a lithium ion battery anode material, which reduces the consumption of a coating material and further improves the performance of the material.
The invention also aims to provide a preparation method of the lithium ion battery anode material, which improves the energy retention rate of the material and is beneficial to the application in the lithium ion battery.
The invention also aims to provide a preparation method of the positive electrode material of the lithium ion battery, which reduces the increase of resistance and is beneficial to the application in the lithium ion battery.
A method for preparing positive electrode material of lithium ion battery adds metal salt of fatty acid of C10-C34, maintains coating uniformity of electrode material prepared by solid phase method, and reduces usage of coating material.
The fatty acid provided by the invention contains at least one carboxyl. Such as: but are not limited to, saturated or unsaturated monoacids, saturated or unsaturated diacids, saturated or unsaturated triacids, and the like, which contain a number of monoatoms greater than 10, especially from 10 to 34, such as: 10. 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, and 34.
Another specific compound embodiment is a saturated fatty acid comprising substituents thereon such as: but are not limited to, hydroxy, mercapto, amino, ester, alkane, alkene, alkyne, and the like.
Another specific compound embodiment is an unsaturated fatty acid comprising at least 1 saturated double or triple bond, and for example: but are not limited to, hydroxy, mercapto, amino, ester, alkane, alkene, alkyne, and like substituents.
In order to enable the lithium ion battery electrode material to have higher thermal stability and cycle life. By utilizing the characteristic that fatty acid contains liquid phase and solid phase at room temperature, namely, the fatty acid is gradually changed from liquid phase to solid phase along with the increase of the carbon chain length of the fatty acid. That is, when the number of carbon atoms of the saturated fatty acid is 10 or more, the fatty acid is in a solid phase at room temperature. Thus, the method can be matched with a method for coating the battery material by the solid phase, has practical feasibility, and can realize more economical and simpler manufacturing of the electrode material.
Another specific fatty acid metal salt embodiment is of formula Me t+ [CH 3 (CH 2 ) n COO] t As shown, n is an integer from 8 to 32, such as: 8. 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 and 32.t is an integer from 1 to 7, such as: 1. 2, 3, 4, 5, 6 and 7.Me is a metal ion such as: but are not limited to, metal ions such as Li, mg, zn, cu, ca, fe, al, ni, co, mn, ti, cr, zr, nb, and W.
When the electrode material is prepared by adopting a solid phase method, the metal salt of the fatty acid is used for coating the lithium ion battery material. Wherein the fatty acid is volatilized during heating, and the metal salt is oxidized at high temperature to form metal oxide (such as but not limited to Li) 2 O,MgO,ZnO,CaO,CuO,NiO,CoO,Al 2 O 3 ,Fe 2 O 3 ,Cr 2 O 3 ,MnO 2 ,TiO 2 ,ZrO 2 ,Nb 2 O 5 And WO 3 Etc.) without any impact on the lithium ion battery material.
When the solid phase method is adopted to prepare the battery material, the metal salts of the various fatty acids can realize coating on the lithium ion battery material, and uniformly distributed oxides are formed on the material, so that the use amount of the adopted coating material is further reduced, for example: less than 1%, such as: but is not limited to 0.5%, also improves the energy retention of the material and reduces the increase in resistance.
As known to the skilled person, the materials used for manufacturing the positive electrode include: layered structure materials such as Li 1± m Ni x Co y Mn z M 1-x-y-z O 2 Shown, wherein M is a trace element such as: but are not limited to Cr, mg, al, ti, zr, zn, ca, nb, W, etc.; m ranges from 0.005 to 0.2; x, y and z are independently selected from any number from 0 to 1, and the sum of x, y and z is 0.8 to 1, such as: but are not limited to x=0.8, y=0.1, z=0.1 or x=0.8, y=0, z=0.15. Common ternary materials are: but is not limited to NCM622 (of the formula LiNi 0.6 Co 0.2 Mn 0.2 O 2 ) NCM811 (chemical formula is LiNi 0.8 Co 0.1 Mn 0.1 O 2 ) And NCA (chemical formula is LiNi 0.8 Co 0.15 Al 0.5 O 2 ) Etc. These materials are used in the present invention either alone or in combination.
The metal salt of fatty acid of the present invention is in the form of a solid powder having a particle diameter of 10nm to 2. Mu.m, particularly a powder having a particle diameter of 10nm to 500 nm.
The metal salts of the fatty acids of the present invention are aluminum stearate and aluminum laurate.
The metal salts of fatty acids of the present invention are magnesium stearate and magnesium laurate.
According to the preparation method of the lithium ion battery anode material, the metal salt of the fatty acid is mixed with the lithium ion battery anode material, and metal oxide is uniformly dispersed on the surface of the lithium ion battery electrode material prepared by sintering (the temperature is 200-1000 ℃).
The form of the positive electrode material of the lithium ion battery, which is applied to the preparation method of the invention, is preferably selected from powder.
According to the preparation method for preparing the lithium ion positive electrode material, provided by the invention, the metal salt of the fatty acid is mixed with the positive electrode material for the lithium battery, and the lithium ion positive electrode material is prepared through high-temperature solid-phase reaction sintering, wherein the sintering temperature is as follows: but not limited to 200-1000 deg.c, sintering time as follows: but are not limited to, 1 hour to 24 hours.
In another method for preparing the lithium ion positive electrode material, the metal salt of the fatty acid is mixed with the positive electrode material for the lithium battery. Heating to 200-1000 ℃ and sintering for 1-24 hours, thereby completing the solid phase reaction of the coating material and the lithium ion battery material. After the sintering reaction is finished, the material is dispersed and sieved, and the anode material which is uniformly coated can be obtained.
According to the various preparation methods provided by the invention, the addition amount of the metal salt is correspondingly determined according to the content (for example, 0.6+/-0.1%) of the metal oxide in the prepared positive electrode material.
In another preparation method for preparing the lithium ion positive electrode material, the metal salt of the fatty acid is mixed with the positive electrode material for the lithium battery, and the lithium ion positive electrode material is prepared by high-temperature solid phase reaction sintering, wherein the metal oxide accounts for the following mass percent: 0.6% ± 0.1%, such as: 0.5%, 0.6% and 0.7%.
In the sintering process, the temperature is raised to 200-1000 ℃ at a speed of 1-10 ℃/min, and then the temperature is kept for 1-24 hours.
In another preparation method of the lithium ion positive electrode material, aluminum stearate or aluminum laurate is mixed with the positive electrode material for the lithium battery, the temperature is raised to 200-1000 ℃ at the speed of 1-10 ℃/min, and the temperature is kept for 1-24 hours, so that the solid phase reaction of the coating material and the lithium ion battery material is completed. After the sintering reaction is finished, the material is dispersed and sieved, and the anode material which is uniformly coated can be obtained.
The specific sintering temperature and sintering time of the preparation method of the invention depend on the decomposition temperature of the fatty acid salt used.
The beneficial effects brought by the invention are as follows:
according to the invention, the metal salt of fatty acid is used as the coating material, and the surface of the positive electrode material can be uniformly coated directly through high-temperature solid phase reaction, so that the method is simple to operate, low in cost and very suitable for large-scale industrial production. After the reaction is finished, no impurity is generated except for the target coating (such as metal oxide) on the surface of the positive electrode material, and the amount of the coating contained in the material is further reduced, so that the performance of the material is further improved.
The preparation method of the lithium battery anode material can rapidly realize uniform coating of the anode material, and enhance the interface stability of the lithium ion battery anode material, thereby enhancing the safety stability and the cycle life of the material, and simultaneously remarkably improving the resistance rise condition of the battery material after use.
Drawings
FIG. 1 is a TGA plot of magnesium stearate;
FIG. 2 is an aluminum stearate TGA graph;
FIG. 3 is an aluminum laurate TGA graph;
FIG. 4 is a surface element analysis chart of comparative example 1;
FIG. 5 is a graph showing the elemental magnesium distribution of the materials prepared in example 1A, example 1B and example 1C;
FIG. 6 is XRD patterns of comparative example 1, comparative example 2, example 1A, example 1B, example 1C and example 2;
fig. 7 is a graph showing charge-discharge curves of materials for a positive electrode of a battery prepared in comparative example 1, comparative example 2, example 1A, example 1B, example 1C, and example 2;
FIG. 8 is a graph showing the DCIR change during cycling of the materials for the positive electrode of the battery prepared in comparative example 1, comparative example 2, example 1A, example 1B, example 1C and example 2;
fig. 9 is a graph showing a cycle performance test of the materials for a battery positive electrode prepared in comparative example 1, comparative example 2, and example 2;
FIG. 10 is XRD patterns of comparative example 3, example 3 and example 4;
fig. 11 is a graph showing charge and discharge curves of materials for a positive electrode of a battery prepared in comparative example 3, example 3 and example 4;
FIG. 12 is XRD patterns of comparative example 4, example 5 and example 6;
fig. 13 is a graph showing charge-discharge curves of materials for a positive electrode of a battery prepared in comparative example 4, example 5 and example 6;
fig. 14 is a graph showing comparison of cycle performance tests of materials for battery positive electrodes prepared in comparative example 4 and example 5.
Detailed Description
The technical scheme of the present invention is described in detail below with reference to the accompanying drawings. The embodiments of the present invention are only for illustrating the technical scheme of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical scheme of the present invention may be modified or substituted without departing from the spirit and scope of the technical scheme of the present invention, and all such modifications are intended to be included in the scope of the claims of the present invention.
The test methods used in the following examples of the present invention are specifically described below:
1) Characterization of X-ray diffraction (XRD) Structure
The testing equipment of X-ray diffraction is Bruce D2-XE-T, the target material used by the instrument is copper target, and the wavelength of X-ray isFirstly weighing 1 g-2 g of sample, spreading the sample at the central position of a sample table as much as possible, and secondly trowelling by using a glass slide to ensure that the sample is level with a sample groove and no sample is outside the groove. And finally, placing the prepared sample stage into a Bruce D2-XE-T for testing, wherein the scanning range of the X-ray 2 theta is set to be 10-80 degrees, the scanning step length is 0.01 degree, and the X-ray exposure time of each step length is 0.1s.
2) Scanning Electron Microscope (SEM) morphology characterization
Firstly, a small amount of powder sample is adhered to a conductive adhesive tape of a sample stage, so that the sample is uniformly dispersed without agglomeration. The sample was then placed in a Japanese electronic Joel JCM-7000NeoScope desktop scanning electron microscope for observation. The elemental analysis of the particle cross section was performed using a Joel JED-2300 energy spectrometer and energy dispersive X-ray spectroscopy (EDS) data was collected.
3) Electrochemical performance test
The prepared lithium ion battery anode material is mixed with a conductive agent (such as carbon black), a binder (such as polyvinylidene fluoride) and a solvent (such as N-methyl pyrrolidone) to prepare electrode slurry, the electrode slurry is coated on an aluminum-based current collector, the electrode slurry is dried to prepare an electrode, the electrode is assembled into a button battery, and an electrochemical test is carried out by using a New wire (CT-4008) battery charge-discharge instrument. Button cells were first cycled 4 turns between 2.75-4.4V using a current of 0.1C, and then cycled using a current of 0.2C or 0.5C over the same voltage interval.
The button cell was tested in a cyclic manner, and at the same time, the button cell was tested for discharge dc resistance (Direct Current Internal Resistance, DCIR).
The method for calculating DCIR by the instrument comprises the following steps: after the charging step is completed, the next step is a rest step, and the voltage (V 1 ) Recording is performed. After the rest step, the next step is a discharging step, the battery is discharged by using constant current (I), and the voltage (V) at the first point of the discharging step 2 ) Recording is performed. The DCIR calculation formula is: dcir= (V 1 -V 2 )/I
4) Thermogravimetric analysis Test (TGA)
Thermogravimetric analysis of the fatty acid salt used was carried out using a PerkinElmer-STA-8000 as the instrument used for the test. Firstly, weighing 6 mg-20 mg of fatty acid salt, placing the fatty acid salt into a crucible, covering the crucible with a cover, and simultaneously placing the crucible with the fatty acid salt and another empty crucible into an instrument furnace. Next, oxygen was flushed into the furnace as a reaction atmosphere, and argon was used as a furnace body shielding gas, and the material was subjected to thermogravimetric analysis experiments using a heating rate of 5 ℃/min to 800 ℃.
Comparative example 1
The positive electrode material NCM523 used in this comparative example has the chemical formula LiNi 0.5 Co 0.2 Mn 0.3 O 2 The material was not subjected to any coating treatment.
The comparative samples were tested for XRD and SEM and EDS characterization, electrochemical cycle life, and DCIR.
Comparative example 2
The positive electrode material NCM523 used in this comparative example has the chemical formula LiNi 0.5 Co 0.2 Mn 0.3 O 2 Simultaneously using stearic acid and nano alumina (Al 2 O 3 )，Al 2 O 3 A coating experiment was performed on NCM523 with a mixture of particle sizes between 20-30 nanometers as coating material.
Firstly, preparing 3g of stearic acid and nano Al 2 O 3 Wherein the mass percentage of stearic acid is controlled to be 3-30%. Ball milling beads of 10g to 30g are added into the mixture to carry out high-speed ball milling, the ball milling time is set to be 1 hour to 5 hours, and the ball milling speed is set to be 100 to 600rmp. After the mixing is finished, collecting stearic acid and nano Al 2 O 3 I.e. the coating material. Appropriate amount of NCM523 is used, and corresponding coating materials (namely stearic acid and nanometer Al are added 2 O 3 Mixture), realize Al 2 O 3 Is 0.5% by mass. NCM523 and coating precursor were placed in a mixer and mixed for 1 to 8 hours. The mixture is heated to 200 ℃ to 1000 ℃ at the speed of 1 ℃ to 10 ℃ per minute, kept at the temperature for 1 hour to 24 hours and then cooled to room temperature along with a furnace to finish the coating process. The comparative samples were tested for electrochemical cycle life and DCIR.
Comparative example 3
The positive electrode material NCM622 used in this comparative example has the chemical formula LiNi 0.6 Co 0.2 Mn 0.2 O 2 The material was not subjected to any coating treatment.
The comparative samples were subjected to XRD, SEM and EDS characterization, electrochemical cycle life, and DCIR testing.
Comparative example 4
The positive electrode material NCM811 used in this comparative example has the chemical formula LiNi 0.8 Co 0.1 Mn 0.1 O 2 The material was not subjected to any coating treatment.
The comparative samples were tested for XRD and SEM and EDS characterization, electrochemical cycle life, and DCIR.
Example 1
The positive electrode material used in this example was NCM523, the same as in comparative example 1, and its chemical formula was LiNi 0.5 Co 0.2 Mn 0.3 O 2 The fatty acid salt used was magnesium stearate (C 36 H 70 MgO 4 )。
Proper amounts of NCM523 and magnesium stearate are placed in a mixer and mixed and stirred for 8 hours to allow the NCM523 and magnesium stearate to be thoroughly mixed.
The mixture was warmed to 650℃at a rate of 5℃per minute and maintained for 10 hours. And then cooling to room temperature along with a furnace, dispersing and sieving the sintered and prepared material, thereby obtaining the final coated anode material, and completing a coating experiment.
The amount of magnesium stearate added was calculated as the amount of magnesium oxide corresponding to the comparative example. The magnesium oxide coated NCM523 is finally prepared in this example by mass percent: 0.5% (labeled: example 1A), 1% (labeled: example 1B) and 2% (labeled: example 1C).
XRD, SEM and EDS characterization, electrochemical cycle life and DCIR testing were performed on the prepared synthesized samples.
Example 2
The positive electrode material used in this example was NCM523, the same as in comparative example 1, and its chemical formula was LiNi 0.5 Co 0.2 Mn 0.3 O 2 The fatty acid salt used was aluminum stearate (C 54 H 105 AlO 6 )。
Proper amounts of NCM523 and aluminum stearate are placed in a mixer, mixed and stirred for 8 hours, and the NCM523 and aluminum stearate are fully mixed.
The mixture was warmed to 650℃at a rate of 5℃per minute and maintained for 10 hours. And then cooling to room temperature along with a furnace, dispersing and sieving the sintered and prepared material, thereby obtaining the final coated anode material, and completing a coating experiment.
The amount of aluminum stearate added was calculated to correspond to the amount of aluminum oxide in the comparative example. In this example, the alumina-coated NCM523 was finally prepared at a mass percentage of 0.5%.
XRD, SEM and EDS characterization, electrochemical cycle life and DCIR testing were performed on the prepared synthesized samples.
Example 3
The positive electrode material used in this example was NCM622, which was the same as that of comparative example 3, and its chemical formula was LiNi 0.6 Co 0.2 Mn 0.2 O 2 The fatty acid salt used was aluminum stearate (C 54 H 105 AlO 6 )。
Proper amounts of NCM622 and aluminum stearate are placed in a mixer and mixed and stirred for 8 hours to allow the NCM622 and aluminum stearate to be thoroughly mixed.
The mixture was warmed to 650℃at a rate of 5℃per minute and maintained for 10 hours. And then cooling to room temperature along with a furnace, dispersing and sieving the sintered and prepared material, thereby obtaining the final coated anode material, and completing a coating experiment.
The amount of aluminum stearate added was calculated to correspond to the amount of aluminum oxide in the comparative example. The alumina-coated NCM622 was finally prepared in this example at a mass percentage of 0.5%.
XRD, SEM and EDS characterization, electrochemical cycle life and DCIR testing were performed on the prepared synthesized samples.
Example 4
The positive electrode material used in this example was NCM622, which was the same as that of comparative example 3, and its chemical formula was LiNi 0.6 Co 0.2 Mn 0.2 O 2 The fatty acid salt used was aluminum laurate (C 36 H 69 AlO 6 )。
Proper amounts of NCM622 and aluminum laurate were placed in a mixer and mixed and stirred for 8 hours to allow the NCM622 and aluminum laurate to be thoroughly mixed.
The mixture is heated to 500 ℃ at a rate of 5 ℃/min and maintained for 10 to 24 hours. And then cooling to room temperature along with a furnace, dispersing and sieving the sintered and prepared material, thereby obtaining the final coated anode material, and completing a coating experiment.
The amount of aluminum laurate added was calculated as the amount of aluminum oxide corresponding to the comparative example. The alumina-coated NCM622 was finally prepared in this example at a mass percentage of 0.5%.
XRD, SEM and EDS characterization, electrochemical cycle life and DCIR testing were performed on the prepared synthesized samples.
Example 5
The positive electrode material used in this example was NCM811 similar to that of comparative example 4, and its chemical formula was LiNi 0.8 Co 0.1 Mn 0.1 O 2 The fatty acid salt used was aluminum stearate (C 54 H 105 AlO 6 )。
Appropriate amounts of NCM811 and aluminum stearate were placed in a mixer and mixed and stirred for 8 hours to allow the NCM811 and aluminum stearate to be thoroughly mixed.
The mixture was warmed to 650℃at a rate of 5℃per minute and maintained for 10 hours. And then cooling to room temperature along with a furnace, dispersing and sieving the sintered and prepared material, thereby obtaining the final coated anode material, and completing a coating experiment.
The amount of aluminum stearate added was calculated to correspond to the amount of aluminum oxide in the comparative example. In this example, the alumina-coated NCM811 was finally prepared at a mass percentage of 0.25%.
XRD, SEM and EDS characterization, electrochemical cycle life and DCIR testing were performed on the prepared synthesized samples.
Example 6
The positive electrode material used in this example was NCM811 similar to that of comparative example 4, and its chemical formula was LiNi 0.8 Co 0.1 Mn 0.1 O 2 The fatty acid salt used was magnesium stearate (C 36 H 70 MgO 4 )。
Appropriate amounts of NCM811 and magnesium stearate were placed in a mixer and mixed and stirred for 8 hours to allow the NCM811 and magnesium stearate to be thoroughly mixed.
The mixture was warmed to 650℃at a rate of 5℃per minute and maintained for 10 hours. And then cooling to room temperature along with a furnace, dispersing and sieving the sintered and prepared material, thereby obtaining the final coated anode material, and completing a coating experiment.
The amount of magnesium stearate added was calculated as the amount of magnesium oxide corresponding to the comparative example. In this example, the magnesium oxide coated NCM811 was finally prepared at a mass percentage of 0.25%.
XRD, SEM and EDS characterization, electrochemical cycle life and DCIR testing were performed on the prepared synthesized samples.
In the above examples of the present invention, three fatty acid salts were used as examples, respectively: magnesium stearate, aluminum stearate and aluminum laurate. The TGA results for these three fatty acid salts are shown in fig. 1-3. In the experiment of thermogravimetric analysis, all three fatty acid salts were decomposed with increasing heating temperature. When the heating temperature is high enough, the weight of the fatty acid salts will remain unchanged, and all fatty acid salts will eventually be converted to the corresponding metal oxides by calculation: when the temperature is greater than 650 ℃, magnesium stearate will eventually become magnesium oxide (as shown in fig. 1), and aluminum stearate will eventually become aluminum oxide (as shown in fig. 2); when the temperature is greater than 500 ℃, the aluminum laurate will eventually become aluminum oxide (as shown in fig. 3). The reaction temperature required for coating the positive electrode material by solid phase reaction using fatty acid salt can be known by thermogravimetric analysis.
SEM/EDS characterization of comparative example 1 was performed, and as shown in fig. 4, only the major elements of nickel, cobalt, and manganese of NCM523 were detected in comparative example 1, and other metal elements were not detected, indicating that comparative example 1 was uncoated NCM523 without magnesium element. SEM/EDS was performed using magnesium stearate coated NCM523 (i.e., example 1A, example 1B, and example 1C), and the major elements nickel, cobalt, and manganese were found, and at the same time, magnesium element in the coated magnesium oxide was observed, as shown in fig. 5, wherein the magnesium elements in example 1A, example 1B, and example 1C were uniformly distributed on the surface of the positive electrode material particles, and as the amount of coating material was increased, the Mg signal was gradually increased, demonstrating that the amount of MgO coating was gradually increased.
As shown in the XRD data of FIG. 6, uncoated NCM523 (i.e., comparative example 1) was a pure R-3m layered structure. The use of fatty acid salts together formed oxide coated NCM523 (i.e., example 1A, example 1B, example 1C, and example 2) was characterized by XRD, also a pure R-3m layered structure. The data indicate that NCM523 coated with fatty acid salts does not produce any impurity. Therefore, the fatty acid salt does not influence the original anode material due to the introduction of a hetero-phase in the coating process.
The electrochemical performance of uncoated NCM523 and NCM523 coated with fatty acid salts was compared. Since the coating material is an oxide and has no electrochemical activity, the charge-discharge capacity of the positive electrode material will be reduced with the increase of the coating mass. As shown in fig. 7, when the charge-discharge curves of the three examples and comparative example 1 are compared, the charge-discharge capacity of NCM523 gradually decreases as the content of MgO in the coating increases. Wherein the charge-discharge capacity of example 1A is comparable to that of comparative example 1. Meanwhile, the MgO-coated NCM523 also shows smaller resistance increase in the cycling process compared with the uncoated NCM523, as shown in FIG. 8, and the positive electrode material coated by the fatty acid salt is proved to show higher interface stability in the electrochemical test. Table 1 summarizes the energy retention of each of the above samples, all NCM523 coated with magnesium stearate had a higher energy retention than uncoated NCM523 over 50 cycles, with NCM523 coated with 0.5% mgo having the highest energy retention of 94.3%. By comparing the initial charge and discharge capacity, the dc resistance increase condition and the energy retention rate, NCM523 (example 1A) coated with 0.5% MgO was achieved using magnesium stearate as the optimal coating condition. Thus, the NCM523 was coated with aluminum stearate to give example 2, still taking a total coating amount of 0.5% oxide. At the same time NCM523 will be coated with stearic acid and alumina to give comparative example 2.
Comparative example 1, comparative example 2 and example 2 were compared. As can be seen by XRD, comparative example 1, comparative example 2 and example 2 are all pure R-3m layered structures (see FIG. 6), and no impurity was found. As can be seen from the electrochemical tests of the three, comparative example 1, comparative example 2 and example 2 all possess comparable initial charge-discharge capacities (see fig. 7); wherein the dc resistance increase of example 2 was minimal (see fig. 8). After 50 cycles, the energy retention of example 2 could reach 95.3%, the sample with the highest energy retention. As shown in fig. 9, the energy retention rate of example 2 was compared with that of comparative example 2, and example 2 had a better energy retention rate. From the comparison of the resistance increase range and the energy retention rate of the positive electrode material, the direct coating of the NCM523 with aluminum stearate has a better effect than the direct coating of the NCM523 with stearic acid and aluminum oxide, and the purpose of further reducing the use amount of the coating material is achieved.
As shown by XRD data in FIG. 10, uncoated NCM622 (comparative example 3) was a pure R-3m layered structure. 0.5% Al for NCM622 using aluminum stearate and aluminum laurate as fatty acid salts 2 O 3 Cladding gives examples 3 and 4, which are characterized by XRD, as well as pure R-3m lamellar structures. The data shows that NCM622 coated with aluminum stearate and aluminum laurate as fatty acid salts did not produce any impurity. Therefore, the fatty acid salt does not influence the original anode material due to the introduction of a hetero-phase in the coating process.
The electrochemical properties of comparative example 3 were compared with those of examples 3 and 4. Since the coating material is an oxide and has no electrochemical activity, the charge-discharge capacity of the positive electrode material will be reduced with the increase of the coating mass. Comparative example 3, example 3 and example 4 charge-discharge curves comparative case referring to fig. 11, the charge-discharge capacities of example 3 and example 4 were slightly decreased with respect to comparative example 3. After 50 cycles, the energy retention rates of example 3 and example 4 can reach 92.2% and 90.8%, respectively, which are higher than 89.2% of comparative example 3. As can be seen from Table 1, after 50 cycles, the resistances of example 3 and example 4 can reach 25.9 ohms and 30.98 ohms, which are lower than 31.76 ohms of comparative example 3.
As shown by XRD data in FIG. 12, uncoated NCM811 (comparative example 4) is a pure R-3m layered structure. And 0.25% Al for NCM811 using aluminum stearate and magnesium stearate as fatty acid salts 2 O 3 And MgO coating gives examples 5 and 6, which are characterized by XRD, as well as pure R-3m layered structures. The data indicate the use of aluminum stearate and magnesium stearate as fatty acidsSalt coated NCM811 did not produce any impurity. Therefore, the fatty acid salt does not influence the original anode material due to the introduction of a hetero-phase in the coating process.
The electrochemical properties of comparative example 4 were compared with those of examples 5 and 6. Although the coating material was oxide and had no electrochemical activity, the coating mass of 0.25% had little effect on the charge-discharge capacity of the positive electrode material NCM 811. Comparative example 4, charge-discharge curves of example 5 and example 6 are compared with reference to fig. 13. The energy retention rates of example 5 and example 6 can reach 88.3% and 85.6%, respectively, over 50 cycles, which are higher than 85.5% of comparative example 4, but the values are reduced compared to example 3 and example 4, indicating that the energy retention rates are inferior to those of example 3 and example 4. Fig. 14 compares the discharge capacities of example 5 and comparative example 4, and the discharge capacity retention rate of example 5 is superior to that of comparative example 4.
TABLE 1 energy retention after 50 cycles of various coated and uncoated cathode materials

Claims (6)

1. A preparation method of a lithium ion battery anode material is characterized in that a metal salt of fatty acid is adopted to be mixed with the anode material for the lithium ion battery, and the coated anode material is prepared by high-temperature solid phase reaction sintering, wherein the metal salt of fatty acid is in the form of solid powder, and the particle size is 10 nm-2 mu m, as shown in formula Me t+ [CH 3 (CH 2 ) n COO] t Wherein n is an integer of 8 to 32, t is an integer of 1 to 7, and Me is a metal ion;
the metal salt is oxidized at high temperature to form metal oxide, and the mass percentage of the metal oxide in the coated positive electrode material is 0.6% +/-0.1%;
the positive electrode material for the lithium battery is selected from one or more of NCM622, NCM811 and NCA.
2. The method according to claim 1, wherein n is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 or 32.
3. The method according to claim 1, wherein the metal ion is selected from the group consisting of Li, mg, zn, cu, ca, fe, al, ni, co, mn, ti, cr, zr, nb and W.
4. The process according to claim 1, wherein the metal salt of fatty acid is selected from the group consisting of aluminum stearate, aluminum laurate, magnesium stearate and magnesium laurate.
5. The method according to claim 1, wherein the solid phase reaction is carried out at a temperature of 200 to 1000 ℃ for 1 to 24 hours.
6. The preparation method according to claim 1, wherein the solid phase reaction is carried out at a rate of 1 to 10 ℃ per minute and then heated to 200 to 1000 ℃ and then kept for 1 to 24 hours.
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