CN108258224B - Ternary positive electrode material with surface coated with metal oxide and preparation method thereof - Google Patents

Ternary positive electrode material with surface coated with metal oxide and preparation method thereof Download PDF

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CN108258224B
CN108258224B CN201810058406.3A CN201810058406A CN108258224B CN 108258224 B CN108258224 B CN 108258224B CN 201810058406 A CN201810058406 A CN 201810058406A CN 108258224 B CN108258224 B CN 108258224B
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metal oxide
cathode material
surface coated
powder
ball milling
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CN108258224A (en
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胡仁宗
陈志伟
鲁忠臣
朱敏
曾美琴
许辉勇
章兴石
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South China University of Technology SCUT
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
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    • 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
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    • 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
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    • 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
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    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention belongs to the technical field of lithium ion battery materials, and discloses a ternary cathode material with a surface coated with metal oxide and a preparation method thereof. According to the method, the ball powder mass ratio and the rotating speed of the ball mill are reasonably adjusted, the ternary cathode material with the surface coated with the metal oxide can be prepared by adopting one-step discharge ball milling without complicated chemical synthesis or heat treatment, the conductivity of the surface of the cathode material is improved, and the reaction of the surface of the cathode and the electrolyte is effectively inhibited, so that the circulation stability of the ternary cathode material is improved, and the ternary cathode material has a good application prospect.

Description

Ternary positive electrode material with surface coated with metal oxide and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium ion battery manufacturing, and particularly relates to a ternary cathode material with a surface coated with metal oxide and a preparation method thereof.
Background
As a novel energy storage device, the lithium ion battery is not only widely applied in the fields of portable electronic devices, smart power grids and the like, but also attracts much attention as a power battery of a new energy automobile. The commercial graphite cathode which is relatively mature in development is particularly urgent for the research and development of a positive electrode material which is high in capacity, long in service life, low in cost, safe and environment-friendly. The anode materials of the lithium ion power battery which is commercially used at present mainly comprise lithium iron phosphate and ternary materials. The lithium iron phosphate technical route is gradually replaced due to the limitation of lower energy density, and ternary materials become the mainstream of the anode materials of the power battery.
At present, most of the ternary cathode materials researched mainly comprise lithium nickel cobalt manganese oxide and lithium nickel cobalt aluminate. The nickel cobalt lithium manganate (NCM) with the layered structure has a good Ni-Co-Mn ternary synergistic effect, and combines the advantages of three materials: LiCoO2Good cycle performance of LiNiO2High specific capacity and LiMnO2The lithium ion battery cathode material has high safety, low cost and the like, and is a positive electrode material which is hopeful to be applied to high-energy and high-power lithium ion batteries. However, many studies have shown that energy storage and release of lithium ion batteries based on a lithium intercalation-deintercalation mechanism is dependent on Li+In the process of embedding and releasing positive and negative electrode materials, the NCM material (especially the high-nickel NCM material) is embedded with lithium and released from lithium for a long time, the large increase of lithium vacancy easily causes cation mixed discharge and crystal structure collapse to cause irreversible capacity loss, meanwhile, the high-temperature and high-pressure working environment in the battery can reduce the stability of the active material, the corrosion action of electrolyte on the positive electrode material in the charging and discharging process is accelerated, so that the harmful phenomena of transition metal dissolution aggravation, large heat release and the like are caused, the cycle performance of the battery is damaged, the safety performance of the battery is also reduced, and the application of the NCM material in practice is limited.
Aiming at the problem of poor cycle stability of NCM materials, the following modification methods are mainly adopted at present: 1) doping elements; 2) coating the surface; 3) and optimizing the synthesis process. Related researches find that the surface structure of the material has a very important influence on the electrochemical performance and the thermal stability of the material. The surface coating layer avoids direct contact between the material and electrolyte, reduces side reactions, and has a remarkable improvement effect on the performance stability of the ternary material. Under the background of large-scale industrial application, the great significance of seeking for an efficient, simple and reliable coating method for modifying the ternary cathode material is achieved.
The Chinese patent application with the publication number of CN105932251A discloses a preparation method and application of a metal oxide coated lithium ion battery anode material, wherein a planetary ball mill or a roller ball mill is adopted to ball-mill and mix metal powder and the anode material, and in order to avoid the generation of overhigh mechanical energy to damage the surface appearance and the internal structure of the anode material, a lower rotating speed (400-800 r/min) is adopted, but the effect of powder is not sufficiently promoted by only depending on a lower mechanical stress field, and the ball milling only plays a role of uniformly mixing powder. Therefore, after the powder is mixed by ball milling, further chemical reaction or heat treatment is required to coat the surface of the positive electrode material with a uniform metal oxide. The coating method needs the working procedures of ball milling, stirring, filtering, drying, heat treatment and the like, has the defects of complex operation process, complicated preparation process, longer time consumption (more than or equal to 20 hours), higher energy consumption and the like, and is not beneficial to being applied to large-scale industrial production.
Chinese patent publication No. CN102185135A discloses a method for preparing a tin-carbon composite material for a negative electrode of a lithium ion battery, and mainly introduces the preparation of tin-carbon composite powder by using a dielectric barrier discharge plasma assisted high-energy ball milling method. In order to improve the ball milling efficiency and achieve the purpose of quickly refining powder, the method adopts the ball powder with the mass ratio of 30: 1-70: 1, the rotating speed of the ball mill is 930-1400 r/min. However, in the coating modification application of the ternary cathode material, the mechanical energy generated by the high-energy ball milling assisted by the dielectric barrier discharge plasma mainly acts on uniformly dispersing the powder rather than efficiently crushing the powder, so that the reference significance of each parameter of the patent is not great, and the scheme has great limitation in the preparation of the cathode material.
Disclosure of Invention
In order to solve the problems of the ternary cathode material, the invention mainly aims to provide a preparation method of the ternary cathode material with a surface coated with metal oxide.
The invention also aims to provide the ternary cathode material with the surface coated with the metal oxide, which is prepared by the preparation method of the ternary cathode material with the surface coated with the metal oxide.
According to the invention, a dielectric barrier discharge plasma auxiliary high-energy ball milling method is adopted, the ternary material precursor and the lithium source are rapidly mixed, the ternary material is obtained through calcination, and the discharge ball milling process is adopted to coat the metal oxide on the surface of the ternary cathode material, so that the conductivity of the surface of the electrode can be effectively improved, the decomposition of the electrolyte on the surface of the electrode can be inhibited, the structural stability of the ternary cathode material can be enhanced, and the cycle performance of the battery can be improved.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a ternary cathode material with a surface coated with metal oxide comprises the following steps:
(1) mixing nickel-cobalt-manganese hydroxide and a lithium source, performing high-energy ball milling assisted by dielectric barrier discharge plasma, calcining in an oxidizing atmosphere, cooling, crushing and sieving to obtain a nickel-cobalt-manganese ternary positive electrode material;
(2) mixing the nickel-cobalt-manganese ternary positive electrode material powder obtained in the step (1) with nanoscale metal oxide powder, and then carrying out dielectric barrier discharge plasma-assisted high-energy ball milling to obtain a ternary positive electrode material with the surface coated with metal oxide;
in the step (1), the vibration rate in the dielectric barrier discharge plasma assisted high-energy ball milling is 1400-1500 r/min, the time is 1-2 h, and the mass ratio of the grinding ball to the total mass of the nickel-cobalt-manganese hydroxide and the lithium source powder is 20: 1-30: 1;
in the step (2), the vibration rate in the dielectric barrier discharge plasma assisted high-energy ball milling is 900-1100 r/min, the ball milling time is 4-10 h, and the mass ratio of the grinding balls to the powder is 5: 1-20: 1, and the diameter of the grinding ball is 4-6 mm.
Preferably, in the step (1), the lithium source is one of lithium carbonate or lithium hydroxide, and the chemical formula of the nickel-cobalt-manganese hydroxide is NixCoyMnz(OH)2Wherein x is more than or equal to 0.3 and less than or equal to 0.8, y is more than or equal to 0.1 and less than or equal to 0.3, z is more than or equal to 0.1 and less than or equal to 0.3, and x + y + z is equal to 1; the molar ratio of the nickel cobalt manganese hydroxide to the lithium source is n (Ni + Co + Mn): n (li) ═ 1: 1.1.
preferably, the oxidizing atmosphere in step (1) is an oxygen atmosphere or an air atmosphere.
Preferably, in the step (1), the calcining temperature is 500-950 ℃, and the calcining time is 8-25 h. Further preferably, the calcining temperature in the step (1) is 600-800 ℃, and the calcining time is 8-15 h.
Preferably, the nanoscale metal oxide powder in step (2) is SnO2、Al2O3、TiO2And ZnO, the particle size distribution of which is 50 to 500 nm.
Preferably, the mass of the nanoscale metal oxide powder in the step (2) accounts for 1-10% of that of the ternary cathode material with the surface coated with the metal oxide.
Preferably, alternating current is adopted for the dielectric barrier discharge plasma assisted high-energy ball milling in the steps (1) and (2), the alternating voltage is 230V, and the alternating current is 1-3A.
Preferably, in the steps (1) and (2), the discharge gas medium used in the discharge ball milling process is an inert gas, which may be one of nitrogen or argon.
The ternary cathode material with the surface coated with the metal oxide is prepared by the preparation method of the ternary cathode material with the surface coated with the metal oxide.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention synthesizes a ternary material with a surface coated with metal oxide, in the process of preparing the ternary material, the dielectric barrier discharge plasma is utilized to assist the high-energy ball milling to mix the precursor and the lithium source, uniform mixing can be rapidly realized, the activation reaction of the powder is accelerated through the synergistic effect of the mechanical energy and the plasma energy, the activity of the powder is improved, the solid phase reaction in the heat treatment is further accelerated, the calcination time is shortened, the calcination temperature is reduced, and the synthesis process of the ternary material is simpler and more efficient, which is incomparable with the common ball milling.
(2) According to the invention, the ternary cathode material and the nanoscale metal oxide are mixed and then subjected to the dielectric barrier discharge plasma-assisted high-energy ball milling method, and the nanoscale metal oxide is coated on the surface of the ternary cathode material, so that the conductivity of the surface of an electrode can be improved, the decomposition reaction of an electrolyte on the surface of the cathode material can be effectively inhibited, the ternary cathode material has better structural stability and higher reversible capacity, and the cycle performance of a battery is improved.
(3) The invention adopts the dielectric barrier discharge plasma auxiliary high-energy ball milling method to prepare the ternary cathode material coated by the metal oxide, and the plasma is generated by pure gas ionization, so that the heat source is pure and clean, no pollution is generated, high-temperature treatment or a complicated chemical treatment process is not needed, the discharge of waste gas and waste liquid is reduced, the reduction and precipitation of the metal during high-temperature treatment can be avoided, the process is simple, the energy consumption is lower, and the industrial production is easy to realize.
(4) The invention adopts a dielectric barrier discharge plasma auxiliary high-energy ball milling method, has high working efficiency, can effectively coat the metal oxide on the surface of the ternary cathode material by one-step discharge ball milling, and has short preparation period (5-10 h). In a high-voltage discharge environment, the mechanical energy and the plasma energy generated in the ball milling process are cooperated, so that high-speed and high-temperature plasma is bombarded on the surface of the powder, and large impact force and heat effect are generated on the surface of the powder, so that the powder is uniformly mixed; meanwhile, high-activity particles of the plasma easily generate adsorption with the powder and cause high-energy activation of the surface of the powder, the diffusion capacity of the powder is improved, the activity of the ball-milled powder is further enhanced by a fresh surface and a large number of defects introduced by mechanical ball milling, the effect of the plasma on the powder is greatly enhanced, the effect of rapidly and efficiently dispersing and activating the reaction powder is achieved, and finally the metal oxide is uniformly and efficiently coated on the surface of the ternary material.
(5) The invention reasonably adjusts the process parameters used by the dielectric barrier discharge plasma auxiliary high-energy ball milling method, and when coating modification is carried out, the generated mechanical energy mainly acts on uniformly dispersing powder by reducing the mass ratio of ball powder and the rotating speed of the ball mill, the surface of the powder is promoted to be activated and react by more utilizing plasma energy, and finally, a layer of oxide is uniformly coated on the surface of the powder on the premise of not damaging the structure of the anode material as much as possible.
(6) The synergistic effect of plasma particle flow, heat flow and mechanical ball milling force in the high-energy ball milling process of the invention plays a part in inhibiting powder agglomeration, so that nano-scale metal oxide particles are uniformly dispersed on a ternary anode material substrate.
Drawings
FIG. 1 is LiNi prepared in example 10.5Co0.2Mn0.3O2XRD pattern of the material;
FIG. 2 is LiNi prepared in example 10.5Co0.2Mn0.3O2A first charge-discharge curve chart under the current of 0.5C;
FIG. 3 is LiNi prepared in example 10.5Co0.2Mn0.3O2@SnO2XRD pattern of the material;
FIG. 4 is LiNi prepared in example 10.5Co0.2Mn0.3O2@SnO2A first charge-discharge curve chart of the material under the current of 0.5C;
FIG. 5 is LiNi prepared in example 10.5Co0.2Mn0.3O2@SnO2A cycle performance curve diagram of the material under the current of 0.5C;
FIG. 6 is LiNi prepared in comparative example 20.5Co0.2Mn0.3O2@SnO2Materials and LiNi prepared in example 10.5Co0.2Mn0.3O2@SnO2A discharge specific capacity comparison graph of the material circulating for 100 weeks under the current of 0.5C;
FIG. 7 is LiNi prepared in example 20.5Co0.2Mn0.3O2@SnO2A first charge-discharge curve chart of the material under the current of 0.5C;
FIG. 8 is LiNi prepared in example 30.5Co0.2Mn0.3O2@SnO2A first charge-discharge curve chart of the material under the current of 0.5C;
FIG. 9 is LiNi prepared in example 40.5Co0.2Mn0.3O2@SnO2A first charge-discharge curve chart of the material under the current of 0.5C;
FIG. 10 is LiNi prepared in example 50.5Co0.2Mn0.3O2@SnO2XRD pattern of the material;
FIG. 11 is LiNi prepared in example 60.5Co0.2Mn0.3O2@TiO2A cycle performance curve diagram of the material under the current of 0.5C;
FIG. 12 is LiNi prepared in example 70.5Co0.2Mn0.3O2@SnO2Back-scattered SEM images of the material;
Detailed Description
The present invention will be further described with reference to specific examples and drawings, but the embodiments of the present invention are not limited thereto.
Example 1
In the preparation method of the ternary cathode material with the surface coated with the metal oxide, the nano-scale metal oxide is SnO2The ternary positive electrode material is LiNi0.5Co0.2Mn0.3O2(hereinafter referred to as NCM523) comprising the steps of:
firstly, a ternary precursor nickel-cobalt-manganese hydroxide { the element molar ratio n (Ni): n (Co): n (mn) ═ 0.5: 0.2: 0.3} with Li2CO3Mixing by adopting a dielectric barrier discharge plasma auxiliary high-energy ball milling method, wherein a ternary precursor and Li2CO3In a molar ratio of n (Ni + Co + Mn): n (li) ═ 1: 1.1, quality of grinding ball and ternary precursor and Li in discharge ball milling process2CO3The total mass ratio of the powder is 20: 1, the vibration speed of the ball mill is 1500r/min, and the ball milling time is 1 h. The obtained mixed powder is put on a tablet pressPressing into blocks with 10MPa force, placing into a porcelain boat, calcining in a tube furnace, heating to 600 ℃ at a speed of 3 ℃/min, keeping the temperature for 4h, heating to 800 ℃ at a speed of 5 ℃/min, keeping the temperature for 6h, slowly cooling along with the furnace, grinding and sieving to obtain the ternary cathode material NCM 523. Then mixing NCM523 powder and SnO2Powder blending of NCM523 powder and SnO2The mass ratio of the powder is 97: 3, ball milling by adopting a dielectric barrier discharge plasma auxiliary high-energy ball milling method, wherein the milling balls and mixed powder (NCM523 powder and SnO)2Powder) in a mass ratio of 5: 1, the speed of the ball mill is 900r/min, the ball milling time is 5h, the diameter of a grinding ball is 4mm, and the SnO with the surface coated with the metal oxide is obtained2The ternary positive electrode material NCM 523.
The dielectric barrier discharge plasma assisted high-energy ball milling method comprises the following specific steps:
(1) filling grinding balls and the proportioned mixture into a ball milling tank;
(2) vacuumizing the ball milling tank through a vacuum valve, and then filling nitrogen into the ball milling tank;
(3) and switching on a power supply of the ball mill, setting the ball milling mode to be an automatic operation mode, setting the ball milling time and the frequency of the ball mill, setting the alternating voltage to be 230V and setting the alternating current to be 1.5A. The ball milling tank is fixed on a ball milling frame to perform the dielectric barrier discharge plasma auxiliary high-energy ball milling.
LiNi prepared in this example0.5Co0.2Mn0.3O2The XRD pattern of the material is shown in figure 1.
LiNi prepared in this example0.5Co0.2Mn0.3O2The material is used for lithium ion batteries: the ternary cathode material NCM523 (LiNi)0.5Co0.2Mn0.3O2) The conductive agent (Super-P) and the binder (PVDF) are mixed according to the mass ratio of 8: 1: 1, coating the mixture on an aluminum foil to prepare an electrode slice, and performing vacuum drying; in an argon atmosphere glove box, a button cell is assembled by using metal lithium as a counter electrode and EC + DMC + FEC as electrolyte for testing. The test conditions were: the charge-discharge multiplying power is tested to be 0.5C, and the cut-off voltage of the charge-discharge is 2.8V-4.4V (vs. Li)+/Li). 0.5 sideThe first charge and discharge curve obtained by the test is shown in figure 2.
LiNi prepared in this example0.5Co0.2Mn0.3O2@SnO2The XRD pattern of the material is shown in figure 3.
LiNi prepared in this example0.5Co0.2Mn0.3O2@SnO2The materials were assembled into button cells for testing. The test conditions were: the tests of the charge and discharge multiplying power of 0.5C, 1C, 2C, 3C and 5C are independently carried out respectively, and the charge and discharge cut-off voltage is 2.8V-4.4V (vs+/Li). The first charge and discharge curve obtained from the 0.5 test is shown in fig. 4. As shown in FIG. 4, the specific first discharge capacity of the composite material prepared in this example is 168.0mAh/g in 0.5C test. The cycle performance graph obtained by the 0.5C test is shown in figure 5, and the graph can show that the specific discharge capacity is kept at 161.1mAh/g after 100 cycles, the capacity retention rate is 95.89% after 100 cycles, and the good cycle stability is shown.
Comparative example 1
Comparative example 1a method for preparing a ternary cathode material with a surface coated with a metal oxide, wherein the nano-scale metal oxide is SnO2The ternary cathode material was LiNi prepared in example 10.5Co0.2Mn0.3O2(hereinafter referred to as NCM523) comprising the steps of:
(1) pretreatment of activated carbon
Adding activated carbon into 0.02mol/L NaOH alkali solution, heating, boiling, filtering, washing, and adding 0.1mol/LHNO3Boiling the solution, filtering, washing and drying;
(2) preparation of SnO by sol-gel method2Colloid
Weighing a certain amount of SnCl4·5H2Dissolving in secondary deionized water containing a small amount of hydrochloric acid and ethanol, stirring at room temperature for 20min, dripping diluted ammonia water into the solution, adjusting the pH value of the solution to about 1.5, and standing for reaction for 5h to obtain stable light blue latex;
(3) preparation of SnO with mass ratio23/7 powder
According to SnO2Mass ratio of/C3/7 will be pretreatedGood activated carbon addition SnO2Stirring the mixture in the colloidal solution for 20h, filtering, washing, drying (80 ℃) to obtain black powder, and putting the sample in N2Activating for 1h at 500 ℃ in a tubular furnace in atmosphere, and grinding to obtain the product containing 30% SnO2SnO of2C black powder;
(4) ball milling mixing and heat treatment
SnO by pressing2The mass ratio of the NCM523 is 3: 97, mixing NCM523 powder with SnO2Mixing the powder/C, and ball milling with a planetary ball mill, wherein the milling balls and the mixed powder (NCM523 powder and SnO)2powder/C) in a mass ratio of 20: 1, the rotating speed of the ball mill is 400r/min, and the ball milling time is 5 h. Transferring the obtained mixed powder into a porcelain boat, placing into a tube furnace, sintering in air atmosphere, heating to 500 deg.C at 5 deg.C/min, keeping the temperature for 5 hr, and naturally cooling to convert C into CO2And SnO2Remaining on the surface of NCM523, directly screening the material by a manual sieve after discharging to obtain SnO with the surface coated with metal oxide2The ternary positive electrode material NCM 523.
The material obtained in comparative example 1 was subjected to cell assembly and test in the same manner and under the same test conditions as in example 1.
After the 100-cycle charge and discharge test at the charge and discharge rates of 0.5C, 1C, 2C, 3C, and 5C, the comparative test results are shown in table 1 below, and it can be found that the composite material prepared in example 1 is superior to comparative example 1 in terms of 100-cycle specific discharge capacity and cycle stability at different charge and discharge rates.
Table 1 capacity retention ratio after 100 cycles of example 1 and comparative example 1 at different charge and discharge rates
Figure BDA0001554542310000091
Comparative example 2
Comparative example 2 preparation method of ternary cathode material with surface coated with metal oxide, grinding ball removal and mixed powder (NCM523 powder and SnO)2Powder) was 30: 1, the rotating speed of the ball mill is 1500r/min, the ball milling time is 5h, the charge-discharge multiplying power is 0.5C, and the charge-discharge cut-off powerThe pressure is 2.8V-4.4V (vs. Li)+Per Li), the same as in example 1.
The test result shows that the composite material LiNi prepared by the comparative example0.5Co0.2Mn0.3O2@SnO2The first reversible capacity of (A) is 160.8 mAh/g. The specific discharge capacity after 100 cycles is kept at 130.6mAh/g, and the specific discharge capacity retention rate after 100 cycles is only 81.22% (tested under the same conditions, LiNi prepared in example 1)0.5Co0.2Mn0.3O2@SnO2The discharge specific capacity retention rate is 95.89% after 100-week circulation. The specific discharge capacity of 100 cycles tested under the condition of 0.5C is compared with that of the example 1 shown in figure 6, and the excessively high ball powder mass ratio and the rotating speed of the ball mill can be found to reduce the cycle stability of the composite material in the charging and discharging processes.
Example 2
In the preparation method of the ternary cathode material with the surface coated with the metal oxide, the grinding balls and the mixed powder (the NCM523 powder and SnO) are used2Powder) in a mass ratio of 20: 1, the rotating speed of the ball mill is 1100r/min, the ball milling time is 5h, the charge-discharge multiplying power is 0.5C, and the charge-discharge cut-off voltage is 2.8V-4.4V (vs. Li)+Per Li), the same as in example 1.
The test result shows that the composite material LiNi prepared by the embodiment0.5Co0.2Mn0.3O2@SnO2The first reversible capacity of the lithium ion battery is 168.7mAh/g, a cycle performance graph obtained by testing under the condition of 0.5C is shown in figure 7, the specific discharge capacity is kept at 155.2mAh/g after 100 cycles, and the capacity retention rate is 92.00% after 100 cycles.
Example 3
In the preparation method of the ternary cathode material with the surface coated with the metal oxide, the grinding balls and the mixed powder (the NCM523 powder and SnO) are used2Powder) in a mass ratio of 20: 1, the rotating speed of the ball mill is 900r/min, the ball milling time is 5h, the charge-discharge multiplying power is 0.5C, and the charge-discharge cut-off voltage is 2.8V-4.3V (vs. Li)+Per Li), the same as in example 1.
The test results show that the composite material prepared in this exampleLiNi0.5Co0.2Mn0.3O2@SnO2The first reversible capacity of the lithium ion battery is 160.4mAh/g, and a first charge-discharge curve chart obtained by testing under the condition of 0.5C is shown in figure 8.
Example 4
In the preparation method of the ternary cathode material with the surface coated with the metal oxide, the NCM523 powder and SnO are removed2The mass ratio of the powder is 98: 2, the charge-discharge multiplying power is 0.5C, and the charge-discharge cut-off voltage is 2.8V-4.3V (vs. Li)+Per Li), the same as in example 1.
The test result shows that the composite material LiNi prepared by the embodiment0.5Co0.2Mn0.3O2@SnO2The first reversible capacity of the lithium ion battery is 155.7mAh/g, and a first charge-discharge curve chart obtained by testing under the condition of 0.5C is shown in figure 9.
Example 5
In the preparation method of the ternary cathode material with the surface coated with the metal oxide, the NCM523 powder and SnO are removed2The mass ratio of the powder is 96: 4, the charge-discharge multiplying power is 0.5C, and the charge-discharge cut-off voltage is 2.8V-4.3V (vs. Li)+Per Li), the same as in example 1.
The test result shows that the composite material LiNi prepared by the embodiment0.5Co0.2Mn0.3O2@SnO2The first reversible capacity of (A) is 158.2 mAh/g. The specific discharge capacity after 100 cycles is kept at 144.9 mAh/g. Prepared LiNi0.5Co0.2Mn0.3O2@SnO2The XRD pattern of the material is shown in figure 10.
Example 6
In the preparation method of the ternary cathode material with the surface coated with the metal oxide, the nano-scale metal oxide is TiO2NCM523 powder and TiO2The mass ratio of the powder is 95: 5, the charge-discharge multiplying power is 0.5C, and the charge-discharge cut-off voltage is 2.8V-4.3V (vs. Li)+Per Li), the same as in example 1.
The test result shows that the composite material LiNi prepared by the embodiment0.5Co0.2Mn0.3O2@TiO2The first reversible capacity of (A) is 160.3 mAh/g. The cycle performance graph obtained by testing under the condition of 0.5C is shown in FIG. 11, the specific discharge capacity is kept at 142.9mAh/g after 100 cycles, and the capacity retention rate is 89.15% after 100 cycles.
Example 7
In the preparation method of the ternary cathode material with the surface coated with the metal oxide, the discharge ball milling time is 10 hours, the charge-discharge multiplying power is 0.5C, and the charge-discharge cutoff voltage is 2.8V-4.3V (vs+Per Li), the same as in example 1.
The test result shows that the composite material LiNi prepared by the embodiment0.5Co0.2Mn0.3O2@SnO2The first reversible capacity of (A) is 164.2 mAh/g. The specific discharge capacity is kept at 147.3mAh/g after 100 cycles, and the capacity retention rate is 89.71% after 100 cycles.
A back scattering SEM image of the ternary cathode material coated with metal oxide prepared in this example is shown in fig. 12, where the metal oxide SnO is ball-milled2The powder is uniformly distributed in LiNi0.5Co0.2Mn0.3O2On the matrix, the aggregation phenomenon is avoided, which is beneficial to effectively inhibiting the decomposition of the electrolyte on the positive interface in the charge-discharge process.
Example 8
In the preparation method of the ternary cathode material with the surface coated with the metal oxide according to the embodiment, the prepared ternary cathode material is changed into LiNi0.6Co0.2Mn0.2O2(oxygen in the atmosphere of calcination), a charge-discharge magnification of 0.5C, and a charge-discharge cutoff voltage of 2.8V-4.3V (vs. Li)+Per Li), the same as in example 1.
The test result shows that the composite material LiNi prepared by the embodiment0.6Co0.2Mn0.2O2@SnO2The first reversible capacity of (A) is 187.3 mAh/g. The discharge capacity after 100 cycles was kept at 174.2 mAh/g.
The above embodiments are only some preferred embodiments of the present invention, but the embodiments of the present invention are not intended to limit the implementation and the scope of the invention, and all equivalent changes, modifications, substitutions, combinations, simplifications made according to the content and principle of the claims of the present invention should be included in the scope of the present invention.

Claims (10)

1. A preparation method of a ternary cathode material with a surface coated with metal oxide is characterized by comprising the following steps:
(1) mixing nickel-cobalt-manganese hydroxide and a lithium source, performing high-energy ball milling assisted by dielectric barrier discharge plasma, calcining in an oxidizing atmosphere, cooling, crushing and sieving to obtain a nickel-cobalt-manganese ternary positive electrode material;
(2) mixing the nickel-cobalt-manganese ternary positive electrode material powder obtained in the step (1) with nanoscale metal oxide powder, and then carrying out dielectric barrier discharge plasma-assisted high-energy ball milling to obtain a ternary positive electrode material with the surface coated with metal oxide;
in the dielectric barrier discharge plasma assisted high-energy ball milling in the step (1), the vibration rate is 1400-1500 r/min, the ball milling time is 1-2 h, and the mass ratio of the grinding ball to the total mass of the nickel-cobalt-manganese hydroxide and the lithium source powder is 20: 1-30: 1;
in the step (2), the vibration rate in the dielectric barrier discharge plasma assisted high-energy ball milling is 900-1100 r/min, the ball milling time is 4-10 h, and the mass ratio of the grinding balls to the total mass of the nickel-cobalt-manganese ternary positive electrode material powder and the nano-scale metal oxide powder is 5: 1-20: 1, the diameter of the grinding ball is 4-6 mm;
wherein the nano-scale metal oxide powder in the step (2) is SnO2、Al2O3、TiO2And ZnO.
2. The method as claimed in claim 1, wherein the lithium source in step (1) is one of lithium carbonate or lithium hydroxide, and the chemical formula of the nickel-cobalt-manganese hydroxide is NixCoyMnz(OH)2Wherein x is more than or equal to 0.5 and less than or equal to 0.8,y is more than or equal to 0.1 and less than or equal to 0.3, z is more than or equal to 0.1 and less than or equal to 0.3, and x + y + z = 1; the molar ratio of the nickel cobalt manganese hydroxide to the lithium source is n (Ni + Co + Mn): n (li) = 1: 1.1.
3. the method for preparing the ternary cathode material with the surface coated with the metal oxide according to claim 1, wherein the oxidizing atmosphere in the step (1) is an oxygen atmosphere or an air atmosphere.
4. The method for preparing the ternary cathode material with the surface coated with the metal oxide according to claim 1, wherein in the step (1), the calcining temperature is 500-950 ℃, and the calcining time is 8-25 h.
5. The method for preparing the ternary cathode material with the surface coated with the metal oxide according to claim 4, wherein the calcining temperature is 600-800 ℃, and the calcining time is 8-15 h.
6. The method for preparing the ternary cathode material with the surface coated with the metal oxide as claimed in claim 1, wherein the particle size distribution of the nanoscale metal oxide powder in the step (2) is 50-500 nm.
7. The method for preparing the ternary cathode material with the surface coated with the metal oxide according to claim 1, wherein the mass of the nanoscale metal oxide powder in the step (2) accounts for 1-10% of the mass of the ternary cathode material with the surface coated with the metal oxide.
8. The method for preparing the ternary cathode material with the surface coated with the metal oxide according to claim 1, wherein in the steps (1) and (2), a discharge gas medium adopted in the process of the dielectric barrier discharge plasma assisted high-energy ball milling is an inert gas.
9. The preparation method of the ternary cathode material with the surface coated with the metal oxide according to claim 1, wherein the dielectric barrier discharge plasma assisted high-energy ball milling in the steps (1) and (2) adopts alternating current, the alternating voltage is 230V, and the alternating current is 1-3A.
10. The ternary cathode material with the surface coated with the metal oxide is characterized by being prepared by the preparation method of the ternary cathode material with the surface coated with the metal oxide as claimed in any one of claims 1 to 9.
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