CN109244447B - Coated nickel cobalt lithium manganate ternary positive electrode material and preparation method and application thereof - Google Patents

Coated nickel cobalt lithium manganate ternary positive electrode material and preparation method and application thereof Download PDF

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CN109244447B
CN109244447B CN201811120920.1A CN201811120920A CN109244447B CN 109244447 B CN109244447 B CN 109244447B CN 201811120920 A CN201811120920 A CN 201811120920A CN 109244447 B CN109244447 B CN 109244447B
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nickel
cobalt
positive electrode
lithium manganate
manganese
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CN109244447A (en
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刘坤
李道聪
丁楚雄
夏昕
汪杰
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Hefei Gotion High Tech Power Energy Co Ltd
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Hefei Guoxuan High Tech Power Energy Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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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Abstract

The invention provides a coated nickel cobalt lithium manganate ternary positive electrode material and a preparation method and application thereof. The method comprises the following steps: mixing nickel salt, cobalt salt and manganese salt, dissolving in water to form a homogeneous solution, and adding urea into the homogeneous solution to dissolve to obtain a mixed solution; carrying out hydrothermal reaction on the mixed solution, filtering, washing and drying to obtain a nickel-cobalt-manganese precursor; adding a lithium source into the nickel-cobalt-manganese precursor, uniformly mixing, heating for reaction, and annealing to obtain a nickel-cobalt-manganese acid lithium ternary positive electrode material; then mixing the lithium nickel cobalt manganese oxide with a coating agent and sintering to obtain a nickel cobalt lithium manganese oxide ternary positive electrode material with an outer layer containing the coating agent; and then adding BP2000 for ball milling, thereby preparing the coated nickel cobalt lithium manganate ternary cathode material. The method is simple and environment-friendly, can realize uniform coating of the anode material, and is easy for large-scale production; the prepared coated nickel cobalt lithium manganate ternary cathode material can meet the requirement of high energy density of a lithium ion battery, and has excellent conductivity and cycling stability.

Description

Coated nickel cobalt lithium manganate ternary positive electrode material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a coated nickel cobalt lithium manganate ternary cathode material as well as a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high voltage, high specific energy, light weight, small volume, small self-discharge, long service life and the like, is one of the battery systems with the best comprehensive performance at present, and is widely applied to high-energy portable electronic equipment. In the civil field, lithium ion batteries are rapidly expanding from the 3C field (notebook computers, smart phones, mobile electronic devices, and the like) to the energy transportation field, including wind power station storage, solar energy, grid peak shaving, electric vehicles, and the like. In the aspect of national defense and military, the application of the lithium ion battery covers various military categories such as land (army chariot, individual system, military communication equipment and the like), sea (underwater robot, submarine), air (unmanned reconnaissance aircraft) and the like. With the rapid expansion of the application range, the lithium ion battery is developing towards a higher energy density (250-300 Wh/kg), the performance of the positive electrode material is a key factor for determining the indexes of the lithium ion battery, such as the energy density, the cycle life and the safety, and the positive electrode material has some defects, which are mainly reflected in high internal impedance and poor stability. Therefore, higher requirements are placed on the safety and cycle life of the battery.
Disclosure of Invention
Based on the defects in the prior art, the invention aims to provide the preparation method of the coated nickel cobalt lithium manganate ternary positive electrode material, which is simple and environment-friendly, can realize uniform coating of the positive electrode material, and is easy for large-scale production; the invention also aims to provide the coated nickel cobalt lithium manganate ternary cathode material prepared by the preparation method, and the coated nickel cobalt lithium manganate ternary cathode material can meet the requirement of high energy density of a lithium ion battery and has excellent conductivity and cycling stability.
The purpose of the invention is realized by the following technical scheme:
on one hand, the invention provides a preparation method of a coated nickel cobalt lithium manganate ternary cathode material, which comprises the following steps:
mixing nickel salt, cobalt salt and manganese salt, dissolving in water to form a homogeneous solution, and adding urea into the homogeneous solution to dissolve to obtain a mixed solution;
performing hydrothermal reaction on the mixed solution, filtering, washing and drying to obtain a nickel-cobalt-manganese precursor;
adding a lithium source into the nickel-cobalt-manganese precursor, uniformly mixing, heating for reaction, and annealing to obtain a nickel-cobalt-manganese acid lithium ternary positive electrode material;
mixing the nickel cobalt lithium manganate ternary positive electrode material with a coating agent, and sintering to obtain a nickel cobalt lithium manganate ternary positive electrode material with an outer layer containing the coating agent;
and fifthly, adding BP2000 into the nickel cobalt lithium manganate ternary positive electrode material with the coating agent on the outer layer for ball milling, thereby preparing the coated nickel cobalt lithium manganate ternary positive electrode material.
In the preparation method, the BP2000 adopts Cabot superconducting carbon BLACK BLACK
Figure BDA0001811261190000021
2000。
In the above preparation method, the capping agent is used to maintain structural stability of the battery cycle.
In the preparation method, urea is not strong in alkalinity and is more favorable for controlling grain growth as a precipitator, the urea is hydrolyzed by matching with hydrothermal reaction, the grain growth can be effectively controlled, and meanwhile, the structural stability and the conductivity can be effectively improved by adopting a two-step double-coating method.
In the above preparation method, preferably, the amount of the urea is 5 to 15 times of the total amount of the nickel salt, the cobalt salt and the manganese salt.
In the above preparation method, preferably, the molar ratio of the nickel salt, the cobalt salt and the manganese salt is (3-8): (1-4): (1-3).
In the above preparation method, preferably, the nickel salt may include one or a combination of more of nickel sulfate, nickel chloride, nickel acetate, nickel nitrate, and the like.
In the above preparation method, preferably, the cobalt salt may include one or a combination of more of cobalt sulfate, cobalt chloride, cobalt acetate, cobalt nitrate, and the like.
In the above preparation method, preferably, the manganese salt may include one or a combination of manganese sulfate, manganese chloride, manganese acetate, manganese nitrate, and the like.
In the above preparation method, preferably, the mass of the lithium source is 1.03 to 1.11 times that of the nickel-cobalt-manganese precursor. The coated nickel cobalt lithium manganate ternary positive electrode material finally prepared by adopting the proportion is more beneficial to exerting the gram capacity of the material.
In the above preparation method, preferably, the lithium source may include one or a combination of more of lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, and the like.
In the preparation method, preferably, the mass of the coating agent is 0.1-0.5% of the mass of the nickel cobalt lithium manganate ternary positive electrode material.
In the above preparation method, preferably, the coating agent may include aluminum fluoride (AlF)3) Polypyrrole (PPy), Polyimide (PI), metal organic framework compounds (MOFs), and the like.
In the above preparation method, preferably, the metal organic framework compound may include one or more of Fe-MOF, Cu-MOF, Mn-MOF and the like in combination.
In the preparation method, preferably, the mass of the BP2000 is 0.1-2% of that of the nickel cobalt lithium manganate ternary positive electrode material with the coating agent in the outer layer.
In the preparation method, preferably, in the second step, the temperature for performing the hydrothermal reaction is 120-180 ℃; the reaction time is 8-24 h.
In the preparation method, preferably, in the third step, the temperature of the heating reaction is 300-; the reaction time is 3-6 h.
In the preparation method, preferably, in the third step, the annealing temperature is 825-845 ℃; the annealing time is 8-12 h.
In the above preparation method, preferably, in the fourth step, the sintering temperature is 400-; the sintering time is 3-6 h.
In the preparation method, preferably, in the step five, a high-energy ball milling method is adopted for ball milling, and the ball-to-material ratio is 10: 1; the ball milling time is 100-; the stirring speed of the ball mill is 500-900 r/min.
In the above preparation method, preferably, the nickel cobalt lithium manganate ternary positive electrode material with an outer layer containing a coating agent prepared in the fourth step further comprises the steps of pre-grinding and fine grinding under a dry condition.
On the other hand, the invention also provides a coated nickel cobalt lithium manganate ternary cathode material which is prepared by adopting the preparation method; the particle size of the coated nickel cobalt lithium manganate ternary cathode material is 8-12 mu m.
On the other hand, the invention also provides application of the coated nickel cobalt lithium manganate ternary cathode material in the field of lithium ion batteries.
The invention has the beneficial effects that:
the coated nickel cobalt lithium manganate ternary positive electrode material prepared by a hydrothermal method and a high-energy ball milling method is simple and convenient to operate, low in raw material cost, environment-friendly and suitable for large-scale production; the urea is adopted as the precipitator, so that the growth of crystal grains is more favorably controlled, and the urea is matched with the hydrothermal reaction for hydrolysis, so that the growth of the crystal grains can be effectively controlled; the nickel cobalt lithium manganate ternary positive electrode material with the coating agent on the outer layer is coupled with the specially-conductive BP2000, so that the charge mass transfer resistance of the battery is reduced, the rapid movement of electrons is promoted, the electrochemical performance of the finally prepared coated nickel cobalt lithium manganate ternary positive electrode material is greatly improved, and a good synergistic effect is achieved.
Drawings
Fig. 1 is an SEM image of a nickel-cobalt-manganese precursor of 3000x magnification in example 2 of the present invention;
fig. 2 is an SEM image of 10000 × (magnification) of the nickel-cobalt-manganese precursor in example 2 of the present invention;
FIG. 3 is an SEM image of 10000x magnification of the coated lithium nickel cobalt manganese oxide ternary positive electrode material in example 2 of the invention;
FIG. 4 is a SEM image of 5000x magnification of the coated lithium nickel cobalt manganese oxide ternary positive electrode material in example 2 of the invention;
FIG. 5 is a graph of specific capacity versus cycle number for the example of the invention and the comparative example under cycling conditions of run 1C.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
The embodiment provides a coated nickel cobalt lithium manganate ternary cathode material LiNi0.33Co0.33Mn0.33O2@AlF3A method for preparing/BP 2000, which comprises the following steps:
step one, adding nickel sulfate, manganese chloride and cobalt acetate into a beaker according to the molar ratio of 3:3:3, mixing and dissolving in deionized water to form a homogeneous solution according to 5n (Ni)2++Co2++Mn2+) Adding urea into the homogeneous solution to dissolve to obtain a mixed solution;
quickly transferring the mixed solution into a 100mL polytetrafluoroethylene lining, carrying out hydrothermal reaction for 8h at 120 ℃, filtering, washing and drying to obtain a nickel-cobalt-manganese precursor;
adding 1.03 times of lithium carbonate into the nickel-cobalt-manganese precursor, fully and uniformly mixing, heating and reacting for 3 hours at 500 ℃, and then annealing for 8 hours at 900 ℃ to obtain the nickel-cobalt-manganese acid lithium ternary positive electrode material LiNi0.33Co0.33Mn0.33O2；
Step four, preparing the lithium nickel cobalt manganese oxide ternary positive electrode material LiNi0.33Co0.33Mn0.33O2With a coating agent AlF3(the amount of addition is LiNi)0.33Co0.33Mn0.33O20.1%) of the nickel cobalt lithium manganate, and sintering at 400 ℃ to obtain the nickel cobalt lithium manganate ternary positive electrode material LiNi with the coating agent on the outer layer0.33Co0.33Mn0.33O2@AlF3；
Step five, the nickel cobalt lithium manganate ternary positive electrode material LiNi containing a coating agent on the outer layer0.33Co0.33Mn0.33O2@AlF3Adding BP2000 (LiNi in the amount of0.33Co0.33Mn0.33O2@AlF30.1%) of the nickel cobalt lithium manganate is subjected to high-energy ball milling, the stirring speed is 500r/min, the ball-to-material ratio is 10:1, and the ball milling time is 100min, so that the coated nickel cobalt lithium manganate ternary cathode material LiNi is prepared0.33Co0.33Mn0.33O2@AlF3/BP2000。
The implementation also provides the coated nickel cobalt lithium manganate ternary positive electrode material LiNi prepared by the preparation method0.33Co0.33Mn0.33O2@AlF3/BP2000。
The implementation also provides the coated nickel cobalt lithium manganate ternary positive electrode material LiNi0.33Co0.33Mn0.33O2@AlF3The application of the/BP 2000 in the field of lithium ion batteries.
Evaluation test of electrochemical Properties
The prepared coated nickel cobalt lithium manganate ternary positive electrode material LiNi0.33Co0.33Mn0.33O2@AlF3And taking the/BP 2000 as a positive electrode, performing a sheet making process in a power-on manufacturing process in a drying room, assembling the positive electrode into a CR2016 button cell in an argon-filled glove box, and performing an electrochemical performance test at room temperature.
The charging and discharging interval is 3.0-4.3V, and the electrochemical performance of the material is evaluated by sequentially carrying out the charging and discharging tests of 0.2C, 1C, 2C and 0.2C once and then carrying out the cycle performance test of 1C.
According to the method experiment of the example 1, the specific discharge capacity of the 1C is 149.03mAh/g for the first time, and after 50 cycles, the specific discharge capacity still reaches 143.07 mAh/g.
Example 2
The embodiment provides a coated nickel cobalt lithium manganate ternary cathode material LiNi0.6Co0.2Mn0.2O2@AlF3A method for preparing/BP 2000, which comprises the following steps:
step one, adding nickel chloride, cobalt nitrate and manganese acetate into a beaker according to the molar ratio of 6:2:2, mixing and dissolving in deionized water to form a homogeneous solution according to the proportion of 10n (Ni)2++Co2++Mn2+) Adding urea into the homogeneous solution to dissolve to obtain a mixed solution;
quickly transferring the mixed solution into a 100mL polytetrafluoroethylene lining, carrying out hydrothermal reaction for 10h at 140 ℃, filtering, washing and drying to obtain a nickel-cobalt-manganese precursor; the SEM images of the nickel-cobalt-manganese precursor with different magnifications are shown in figures 1 and 2, and it can be seen from figures 1 and 2 that the sphericity is relatively uniform, stable and better.
Step three, adding 1.05 times of lithium hydroxide into the nickel-cobalt-manganese precursor, fully and uniformly mixing, heating and reacting for 5 hours at 500 ℃, and then annealing for 9 hours at 900 ℃ to obtain the nickel-cobalt-manganese acid lithium ternary positive electrode material LiNi0.6Co0.2Mn0.2O2；
Step four, preparing the lithium nickel cobalt manganese oxide ternary positive electrode material LiNi0.6Co0.2Mn0.2O2With a coating agent AlF3(the amount of addition is LiNi)0.6Co0.2Mn0.2O20.5%) of the nickel cobalt lithium manganate, and sintering at 500 ℃ to obtain the nickel cobalt lithium manganate ternary cathode material LiNi with the coating agent on the outer layer0.6Co0.2Mn0.2O2@AlF3；
Step five, the nickel cobalt lithium manganate ternary positive electrode material LiNi containing a coating agent on the outer layer0.6Co0.2Mn0.2O2@AlF3Adding BP2000 (LiNi in the amount of0.6Co0.2Mn0.2O2@AlF30.5%) of the nickel cobalt manganese oxide powder, firstly pre-grinding for 60min at low speed (120r/min) with the ball-material ratio of 10:1, grinding the added powder into fine powder, then carrying out fine grinding at high speed (600r/min) with the ball-grinding time of 120min, thereby preparing the coated nickel cobalt manganese oxide ternary cathode material LiNi0.6Co0.2Mn0.2O2@AlF3A particle size of 11.2 μm/BP 2000.
The implementation also provides the coated nickel cobalt lithium manganate ternary positive electrode material LiNi prepared by the preparation method0.6Co0.2Mn0.2O2@AlF3a/BP 2000; the LiNi0.6Co0.2Mn0.2O2@AlF3SEM images of different magnifications of/BP2000 are shown in FIGS. 3 and 4, and it can be seen from FIGS. 3 and 4 that: the surface of the particles is indeed coated with AlF before and after coating3Coated with a material that couples with BP 2000.
The implementation also provides the coated nickel cobalt lithium manganate ternary positive electrode material LiNi0.6Co0.2Mn0.2O2@AlF3The application of the/BP 2000 in the field of lithium ion batteries.
Evaluation test of electrochemical Properties
The prepared coated nickel cobalt lithium manganate ternary positive electrode material LiNi0.6Co0.2Mn0.2O2@AlF3And taking the/BP 2000 as a positive electrode, performing a sheet making process in a power-on manufacturing process in a drying room, assembling the positive electrode into a CR2016 button cell in an argon-filled glove box, and performing an electrochemical performance test at room temperature.
The charging and discharging interval is 3.0-4.3V, and the electrochemical performance of the material is evaluated by sequentially carrying out the charging and discharging tests of 0.2C, 1C, 2C and 0.2C once and then carrying out the cycle performance test of 1C.
According to the method experiment of the example 2, the specific discharge capacity of the 1C is 166.1mAh/g, and 163.5mAh/g is still achieved after 50 cycles.
Example 3
The embodiment provides a coated nickel cobalt lithium manganate ternary cathode material LiNi0.5Co0.2Mn0.3O2@AlF3A method for preparing/BP 2000, which comprises the following steps:
step one, adding nickel acetate, cobalt sulfate and manganese chloride into a beaker according to the molar ratio of 5:2:3, mixing and dissolving in deionized water to form a homogeneous solution according to the proportion of 15n (Ni)2++Co2++Mn2+) Adding urea into the homogeneous solution to dissolve to obtain a mixed solution;
quickly transferring the mixed solution into a 100mL polytetrafluoroethylene lining, carrying out hydrothermal reaction for 16h at 160 ℃, filtering, washing and drying to obtain a nickel-cobalt-manganese precursor;
adding 1.07 times of lithium acetate into the nickel-cobalt-manganese precursor, fully and uniformly mixing, heating and reacting for 4h at 500 ℃, and then annealing for 12h at 900 ℃ to obtain the nickel-cobalt-manganese acid lithium ternary positive electrode material LiNi0.5Co0.2Mn0.3O2；
Step four, preparing the lithium nickel cobalt manganese oxide ternary positive electrode material LiNi0.5Co0.2Mn0.3O2With a coating agent AlF3(the amount of addition is LiNi)0.5Co0.2Mn0.3O20.3%) of the nickel cobalt lithium manganate, and sintering at 700 ℃ to obtain the nickel cobalt lithium manganate ternary cathode material LiNi with the coating agent on the outer layer0.5Co0.2Mn0.3O2@AlF3；
Step five, the nickel cobalt lithium manganate ternary positive electrode material LiNi containing a coating agent on the outer layer0.5Co0.2Mn0.3O2@AlF3Adding BP2000 (LiNi in the amount of0.5Co0.2Mn0.3O2@AlF31%) is subjected to high-energy ball milling, the stirring speed is 700r/min, the ball-to-material ratio is 10:1, and the ball milling time is 125min, so that the coated nickel cobalt lithium manganate ternary cathode material LiNi is prepared0.5Co0.2Mn0.3O2@AlF3/BP2000。
The implementation also provides the coated nickel cobalt lithium manganate ternary positive electrode material LiNi0.5Co0.2Mn0.3O2@AlF3The application of the/BP 2000 in the field of lithium ion batteries.
Evaluation test of electrochemical Properties
The prepared coated nickel cobalt lithium manganate ternary positive electrode material LiNi0.5Co0.2Mn0.3O2@AlF3And taking the/BP 2000 as a positive electrode, performing a sheet making process in a power-on manufacturing process in a drying room, assembling the positive electrode into a CR2016 button cell in an argon-filled glove box, and performing an electrochemical performance test at room temperature.
The charging and discharging interval is 3.0-4.3V, and the electrochemical performance of the material is evaluated by sequentially carrying out the charging and discharging tests of 0.2C, 1C, 2C and 0.2C once and then carrying out the cycle performance test of 1C.
According to the method experiment of the embodiment 3, the specific discharge capacity of the 1C is 160.2mAh/g, and 157.47mAh/g is still achieved after 50 cycles.
Example 4
The embodiment provides a coated nickel cobalt lithium manganate ternary cathode material LiNi0.8Co0.1Mn0.1O2@AlF3A method for preparing/BP 2000, which comprises the following steps:
step one, adding nickel nitrate, cobalt chloride and manganese acetate into a beaker according to the molar ratio of 8:1:1, mixing and dissolving in deionized water to form a homogeneous solution according to 12n (Ni)2++Co2++Mn2+) Adding urea into the homogeneous solution to dissolve to obtain a mixed solution;
step two, quickly transferring the mixed solution into a 100mL polytetrafluoroethylene lining, carrying out hydrothermal reaction for 24h at 180 ℃, filtering, washing and drying to obtain a nickel-cobalt-manganese precursor;
adding 1.11 times of lithium nitrate into the nickel-cobalt-manganese precursor, fully and uniformly mixing, heating and reacting for 6 hours at 500 ℃, and then annealing for 10 hours at 900 ℃ to obtain the nickel-cobalt-manganese acid lithium ternary positive electrode material LiNi0.8Co0.1Mn0.1O2；
Step four, preparing the lithium nickel cobalt manganese oxide ternary positive electrode material LiNi0.8Co0.1Mn0.1O2With a coating agent AlF3(the amount of addition is LiNi)0.8Co0.1Mn0.1O20.2%) of the nickel cobalt lithium manganate, and sintering at 600 ℃ to obtain the nickel cobalt lithium manganate ternary positive electrode material LiNi with the coating agent on the outer layer0.8Co0.1Mn0.1O2@AlF3；
Step five, the nickel cobalt lithium manganate ternary positive electrode material LiNi containing a coating agent on the outer layer0.8Co0.1Mn0.1O2@AlF3Adding BP2000 (LiNi in the amount of0.8Co0.1Mn0.1O2@AlF32%) is subjected to high-energy ball milling, the stirring speed is 900r/min, the ball-to-material ratio is 10:1, and the ball milling time is 150min, so that the coated nickel cobalt lithium manganate ternary cathode material LiNi is prepared0.8Co0.1Mn0.1O2@AlF3/BP2000。
The embodiment also provides a coated nickel cobalt lithium manganate ternary cathode material LiNi0.8Co0.1Mn0.1O2@AlF3BP2000 in lithiumApplication in the field of ion batteries.
Evaluation test of electrochemical Properties
The prepared coated nickel cobalt lithium manganate ternary positive electrode material LiNi0.8Co0.1Mn0.1O2@AlF3And taking the/BP 2000 as a positive electrode, performing a sheet making process in a power-on manufacturing process in a drying room, assembling the positive electrode into a CR2016 button cell in an argon-filled glove box, and performing an electrochemical performance test at room temperature.
The charging and discharging interval is 3.0-4.3V, and the electrochemical performance of the material is evaluated by sequentially carrying out the charging and discharging tests of 0.2C, 1C, 2C and 0.2C once and then carrying out the cycle performance test of 1C.
According to the method experiment of the embodiment, the specific discharge capacity of 1C is 179.5mAh/g, and after 50 cycles, the specific discharge capacity still reaches 172.86 mAh/g.
Example 5
The embodiment provides a coated nickel cobalt lithium manganate ternary cathode material LiNi0.6Co0.2Mn0.2O2A process for the preparation of @ PPy/BP2000, comprising the steps of:
step one, adding nickel sulfate, manganese chloride and cobalt acetate into a beaker according to the molar ratio of 6:2:2, mixing and dissolving in deionized water to form a homogeneous solution according to 5n (Ni)2++Co2++Mn2+) Adding urea into the homogeneous solution to dissolve to obtain a mixed solution;
quickly transferring the mixed solution into a 100mL polytetrafluoroethylene lining, carrying out hydrothermal reaction for 8h at 120 ℃, filtering, washing and drying to obtain a nickel-cobalt-manganese precursor;
adding 1.03 times of lithium carbonate into the nickel-cobalt-manganese precursor, fully and uniformly mixing, heating and reacting for 3 hours at 500 ℃, and then annealing for 8 hours at 900 ℃ to obtain the nickel-cobalt-manganese acid lithium ternary positive electrode material LiNi0.6Co0.2Mn0.2O2；
Step four, preparing the lithium nickel cobalt manganese oxide ternary positive electrode material LiNi0.6Co0.2Mn0.2O2And coating agent polypyrrole (PPy) (LiNi is added in quantity)0.6Co0.2Mn0.2O20.1%) of the nickel cobalt lithium manganate, and sintering at 400 ℃ to obtain the nickel cobalt lithium manganate ternary positive electrode material LiNi with the coating agent on the outer layer0.6Co0.2Mn0.2O2@PPy；
Step five, the nickel cobalt lithium manganate ternary positive electrode material LiNi containing a coating agent on the outer layer0.6Co0.2Mn0.2O2@ PPy to which BP2000 (in LiNi) was added0.6Co0.2Mn0.2O20.1% of @ PPy) is subjected to high-energy ball milling, the stirring speed is 500r/min, the ball-to-material ratio is 10:1, and the ball milling time is 100min, so that the coated nickel cobalt lithium manganate ternary cathode material LiNi is prepared0.6Co0.2Mn0.2O2@PPy/BP2000。
The implementation also provides the coated nickel cobalt lithium manganate ternary positive electrode material LiNi0.6Co0.2Mn0.2O2Application of @ PPy/BP2000 in the field of lithium ion batteries.
Evaluation test of electrochemical Properties
The prepared coated nickel cobalt lithium manganate ternary positive electrode material LiNi0.6Co0.2Mn0.2O2The @ PPy/BP2000 is used as a positive electrode, a sheet making process in the electricity making process is carried out in a drying room, a CR2016 button cell is assembled in an argon-filled glove box, and electrochemical performance test is carried out at room temperature.
The charging and discharging interval is 3.0-4.3V, and the electrochemical performance of the material is evaluated by sequentially carrying out the charging and discharging tests of 0.2C, 1C, 2C and 0.2C once and then carrying out the cycle performance test of 1C.
According to the method experiment of the embodiment, the first discharge specific capacity of 1C is 164.8mAh/g, and the first discharge specific capacity still reaches 162.3mAh/g after 50 cycles.
Example 6
The embodiment provides a coated nickel cobalt lithium manganate ternary cathode material LiNi0.6Co0.2Mn0.2O2A preparation method of @ PI/BP2000 comprises the following steps:
step one, nickel sulfate, manganese chloride andadding cobalt acetate into a beaker according to the molar ratio of 6:2:2, mixing and dissolving in deionized water to form a homogeneous solution according to the proportion of 5n (Ni)2++Co2++Mn2+) Adding urea into the homogeneous solution to dissolve to obtain a mixed solution;
quickly transferring the mixed solution into a 100mL polytetrafluoroethylene lining, carrying out hydrothermal reaction for 8h at 120 ℃, filtering, washing and drying to obtain a nickel-cobalt-manganese precursor;
adding 1.03 times of lithium carbonate into the nickel-cobalt-manganese precursor, fully and uniformly mixing, heating and reacting for 3 hours at 500 ℃, and then annealing for 8 hours at 900 ℃ to obtain the nickel-cobalt-manganese acid lithium ternary positive electrode material LiNi0.6Co0.2Mn0.2O2；
Step four, preparing the lithium nickel cobalt manganese oxide ternary positive electrode material LiNi0.6Co0.2Mn0.2O2And coating agent Polyimide (PI) (LiNi is added in quantity)0.6Co0.2Mn0.2O20.1%) of the nickel cobalt lithium manganate, and sintering at 400 ℃ to obtain the nickel cobalt lithium manganate ternary positive electrode material LiNi with the coating agent on the outer layer0.6Co0.2Mn0.2O2@PI；
Step five, the nickel cobalt lithium manganate ternary positive electrode material LiNi containing a coating agent on the outer layer0.6Co0.2Mn0.2O2Adding BP2000 (LiNi in quantity) into @ PI0.6Co0.2Mn0.2O20.1% of @ PI) is subjected to high-energy ball milling, the stirring speed is 500r/min, the ball-to-material ratio is 10:1, and the ball milling time is 100min, so that the coated nickel cobalt lithium manganate ternary cathode material LiNi is prepared0.6Co0.2Mn0.2O2@PI/BP2000。
The implementation also provides the coated nickel cobalt lithium manganate ternary positive electrode material LiNi0.6Co0.2Mn0.2O2The application of @ PI/BP2000 in the field of lithium ion batteries.
Evaluation test of electrochemical Properties
The prepared coated nickel cobalt lithium manganate ternary positive electrode material LiNi0.6Co0.2Mn0.2O2The @ PI/BP2000 is used as a positive electrode, a sheet making process in a power buckling manufacturing process is carried out in a drying room, a CR2016 button cell is assembled in an argon-filled glove box, and electrochemical performance test is carried out at room temperature.
The charging and discharging interval is 3.0-4.3V, and the electrochemical performance of the material is evaluated by sequentially carrying out the charging and discharging tests of 0.2C, 1C, 2C and 0.2C once and then carrying out the cycle performance test of 1C.
According to the method experiment of the embodiment, the first discharge specific capacity of 1C is 164.1mAh/g, and the first discharge specific capacity still reaches 161.1mAh/g after 50 cycles.
Example 7
The embodiment provides a coated nickel cobalt lithium manganate ternary cathode material LiNi0.6Co0.2Mn0.2O2A method of preparing @ Fe-MOF/BP2000, comprising the steps of:
step one, adding nickel sulfate, manganese chloride and cobalt acetate into a beaker according to the molar ratio of 6:2:2, mixing and dissolving in deionized water to form a homogeneous solution according to 5n (Ni)2++Co2++Mn2+) Adding urea into the homogeneous solution to dissolve to obtain a mixed solution;
quickly transferring the mixed solution into a 100mL polytetrafluoroethylene lining, carrying out hydrothermal reaction for 8h at 120 ℃, filtering, washing and drying to obtain a nickel-cobalt-manganese precursor;
adding 1.03 times of lithium carbonate into the nickel-cobalt-manganese precursor, fully and uniformly mixing, heating and reacting for 3 hours at 500 ℃, and then annealing for 8 hours at 900 ℃ to obtain the nickel-cobalt-manganese acid lithium ternary positive electrode material LiNi0.6Co0.2Mn0.2O2；
Step four, preparing the lithium nickel cobalt manganese oxide ternary positive electrode material LiNi0.6Co0.2Mn0.2O2With a coating agent metal organic framework compound (Fe-MOF) (the addition amount is LiNi)0.6Co0.2Mn0.2O20.1%) of the nickel cobalt lithium manganate, and sintering at 400 ℃ to obtain the nickel cobalt lithium manganate ternary positive electrode material LiNi with the coating agent on the outer layer0.6Co0.2Mn0.2O2@Fe-MOF；
Step five, the nickel cobalt lithium manganate ternary positive electrode material LiNi containing a coating agent on the outer layer0.6Co0.2Mn0.2O2Adding BP2000 (LiNi in the amount of) into @ Fe-MOF0.6Co0.2Mn0.2O20.1% of @ Fe-MOF) is subjected to high-energy ball milling, the stirring speed is 500r/min, the ball-to-material ratio is 10:1, and the ball milling time is 100min, so that the coated nickel cobalt lithium manganate ternary cathode material LiNi is prepared0.6Co0.2Mn0.2O2@Fe-MOF/BP2000。
The embodiment also provides a coated nickel cobalt lithium manganate ternary cathode material LiNi0.6Co0.2Mn0.2O2The application of @ Fe-MOF/BP2000 in the field of lithium ion batteries.
Evaluation test of electrochemical Properties
The prepared coated nickel cobalt lithium manganate ternary positive electrode material LiNi0.6Co0.2Mn0.2O2The @ Fe-MOF/BP2000 is used as a positive electrode, a sheet making process of a power buckling manufacturing process is carried out in a drying room, a CR2016 button cell is assembled in an argon-filled glove box, and electrochemical performance test is carried out at room temperature.
The charging and discharging interval is 3.0-4.3V, and the electrochemical performance of the material is evaluated by sequentially carrying out the charging and discharging tests of 0.2C, 1C, 2C and 0.2C once and then carrying out the cycle performance test of 1C.
According to the method experiment of the embodiment, the first discharge specific capacity of 1C is 165.4mAh/g, and the first discharge specific capacity still reaches 162.3mAh/g after 50 cycles.
Comparative example 1
The comparative example provides a coated nickel cobalt lithium manganate ternary positive electrode material LiNi0.6Co0.2Mn0.2O2The preparation method comprises the following steps:
step one, adding nickel chloride, cobalt nitrate and manganese acetate into a beaker according to the molar ratio of 6:2:2, mixing and dissolving in deionized water to form a homogeneous solution according to the proportion of 10n (Ni)2++Co2++Mn2+) Adding urea into the homogeneous solution to dissolveMixing the solution;
and step two, quickly transferring the mixed solution into a 100mL polytetrafluoroethylene lining, carrying out hydrothermal reaction for 10h at 140 ℃, filtering, washing and drying to obtain the nickel-cobalt-manganese precursor.
Step three, adding 1.05 times of lithium hydroxide into the nickel-cobalt-manganese precursor, fully and uniformly mixing, heating and reacting for 5 hours at 500 ℃, and then annealing for 9 hours at 900 ℃ to obtain the nickel-cobalt-manganese acid lithium ternary positive electrode material LiNi0.6Co0.2Mn0.2O2For comparison.
According to the method experiment of the comparative example 1, the specific discharge capacity of the 1C is 166.4mAh/g, and after 50 cycles, the specific discharge capacity is reduced to 149.3 mAh/g.
Comparative example 2
The comparative example provides a coated nickel cobalt lithium manganate ternary positive electrode material LiNi0.6Co0.2Mn0.2O2@AlF3A method for preparing/BP 2000, which comprises the following steps:
step one, adding nickel chloride, cobalt nitrate and manganese acetate into a beaker according to the molar ratio of 6:2:2, mixing and dissolving in deionized water to form a homogeneous solution according to the proportion of 10n (Ni)2++Co2++Mn2+) Adding NaOH solution into the homogeneous solution, stirring and reacting for 1h, filtering, washing and drying to obtain a nickel-cobalt-manganese precursor;
step two, adding 1.05 times of lithium hydroxide into the nickel-cobalt-manganese precursor, fully and uniformly mixing, heating and reacting for 5 hours at 500 ℃, and then annealing for 9 hours at 900 ℃ to obtain the nickel-cobalt-manganese acid lithium ternary positive electrode material LiNi0.6Co0.2Mn0.2O2；
Step three, preparing the lithium nickel cobalt manganese oxide ternary positive electrode material LiNi0.6Co0.2Mn0.2O2With a coating agent AlF3(the amount of addition is LiNi)0.6Co0.2Mn0.2O20.5%) of the nickel cobalt lithium manganate, and sintering at 500 ℃ to obtain the nickel cobalt lithium manganate ternary cathode material LiNi with the coating agent on the outer layer0.6Co0.2Mn0.2O2@AlF3；
Step four, the nickel cobalt lithium manganate ternary positive electrode material LiNi containing a coating agent on the outer layer0.6Co0.2Mn0.2O2@AlF3Adding BP2000 (LiNi in the amount of0.6Co0.2Mn0.2O2@AlF30.5%) of the nickel cobalt lithium manganate is subjected to high-energy ball milling with a ball-to-material ratio of 10:1, and high-speed (600r/min) fine milling is performed for 120min, so that the coated nickel cobalt lithium manganate ternary positive electrode material LiNi is prepared0.6Co0.2Mn0.2O2@AlF3/BP2000。
The comparative example also provides the coated nickel cobalt lithium manganate ternary positive electrode material LiNi0.6Co0.2Mn0.2O2@AlF3The application of the/BP 2000 in the field of lithium ion batteries.
Evaluation test of electrochemical Properties
The prepared coated nickel cobalt lithium manganate ternary positive electrode material LiNi0.6Co0.2Mn0.2O2@AlF3And taking the/BP 2000 as a positive electrode, performing a sheet making process in a power-on manufacturing process in a drying room, assembling the positive electrode into a CR2016 button cell in an argon-filled glove box, and performing an electrochemical performance test at room temperature.
The charging and discharging interval is 3.0-4.3V, and the electrochemical performance of the material is evaluated by sequentially carrying out the charging and discharging tests of 0.2C, 1C, 2C and 0.2C once and then carrying out the cycle performance test of 1C.
According to the method experiment of the comparative example 2, the first discharge specific capacity of 1C is measured to be 158.4mAh/g, and the first discharge specific capacity still reaches 155.2mAh/g after 50 cycles.
Comparative example 3
The comparative example provides a coated nickel cobalt lithium manganate ternary positive electrode material LiNi0.6Co0.2Mn0.2O2@AlF3A method for preparing/BP 2000, which comprises the following steps:
step one, adding nickel chloride, cobalt nitrate and manganese acetate into a beaker according to the molar ratio of 6:2:2, mixing and dissolving in deionized water to form a homogeneous solution according to the proportion of 10n (Ni)2++Co2++Mn2+) To homogeneous solutionAdding urea into the solution to dissolve to obtain a mixed solution;
quickly transferring the mixed solution into a 100mL polytetrafluoroethylene lining, carrying out hydrothermal reaction for 10h at 140 ℃, filtering, washing and drying to obtain a nickel-cobalt-manganese precursor;
adding 1.0 time of lithium hydroxide into the nickel-cobalt-manganese precursor, fully and uniformly mixing, heating and reacting for 5 hours at 500 ℃, and then annealing for 9 hours at 900 ℃ to obtain the nickel-cobalt-manganese acid lithium ternary positive electrode material LiNi0.6Co0.2Mn0.2O2；
Step four, preparing the lithium nickel cobalt manganese oxide ternary positive electrode material LiNi0.6Co0.2Mn0.2O2With a coating agent AlF3(the amount of addition is LiNi)0.6Co0.2Mn0.2O20.5%) of the nickel cobalt lithium manganate, and sintering at 500 ℃ to obtain the nickel cobalt lithium manganate ternary cathode material LiNi with the coating agent on the outer layer0.6Co0.2Mn0.2O2@AlF3；
Step five, the nickel cobalt lithium manganate ternary positive electrode material LiNi containing a coating agent on the outer layer0.6Co0.2Mn0.2O2@AlF3Adding BP2000 (LiNi in the amount of0.6Co0.2Mn0.2O2@AlF30.5%) of the nickel cobalt lithium manganate is subjected to high-energy ball milling with a ball-to-material ratio of 10:1, and high-speed (600r/min) fine milling is performed for 120min, so that the coated nickel cobalt lithium manganate ternary positive electrode material LiNi is prepared0.6Co0.2Mn0.2O2@AlF3/BP2000。
The comparative example also provides the coated nickel cobalt lithium manganate ternary positive electrode material LiNi0.6Co0.2Mn0.2O2@AlF3The application of the/BP 2000 in the field of lithium ion batteries.
Evaluation test of electrochemical Properties
The prepared coated nickel cobalt lithium manganate ternary positive electrode material LiNi0.6Co0.2Mn0.2O2@AlF3the/BP 2000 is taken as a positive electrode and is carried out in a drying roomAnd a sheet making process in the electricity-fastening manufacturing process and a CR2016 button cell assembled in an argon-filled glove box are subjected to electrochemical performance test at room temperature.
The charging and discharging interval is 3.0-4.3V, and the electrochemical performance of the material is evaluated by sequentially carrying out the charging and discharging tests of 0.2C, 1C, 2C and 0.2C once and then carrying out the cycle performance test of 1C.
According to the method experiment of the comparative example 3, the specific discharge capacity of 1C is 158.3mAh/g, and after 50 cycles, the specific discharge capacity still reaches 154.6 mAh/g.
The experimental results of the examples and comparative examples are shown in table 1 and fig. 5.
Table 1:
sample name Head charger 0.2C ICE 1C 2C 0.2C 1C(1st) 1C(50th) 50th@1C
Example 2 198.6 176.5 88.87％ 165.4 159.8 176.7 166.1 163.5 98.43％
Example 5 197.5 175.4 88.81％ 164.4 158.3 175.8 164.8 162.3 98.48％
Example 6 196.4 173.4 88.29％ 163.5 158.4 174.9 164.1 161.1 98.17％
Example 7 197.2 174.9 88.69％ 164.5 158.6 175.8 165.4 162.3 98.13％
Comparative example 1 201.7 178.1 88.30％ 164.2 159.3 176.4 166.4 149.3 89.72％
Comparative example 2 196.7 169.1 85.96％ 157.07 150.37 169.38 158.4 155.2 97.98％
Comparative example 3 195.5 168.3 86.08％ 157.53 151.65 168.98 158.3 154.6 97.67％
From the experimental data in table 1 and fig. 5, it can be seen that after the ternary material subjected to double coating modification is subjected to 1C cycle for 50 times, the capacity retention rate is greater than 98%, and the uncoated capacity retention rate is only 89%, which illustrates the cycling stability of the coated nickel cobalt lithium manganate ternary positive electrode material of the present invention compared with the electrochemical performance; compared with the comparative example 2, the material prepared by adopting urea as a precipitator and a hydrothermal method has high first effect and good gram capacity exertion; compared with comparative example 3, the low lithium content is not favorable for exerting the gram capacity of the material.
In conclusion, the coated nickel cobalt lithium manganate ternary positive electrode material prepared by a hydrothermal method and a high-energy ball milling method is simple and convenient to operate, low in raw material cost, environment-friendly and suitable for large-scale production; the urea is adopted as the precipitator, so that the growth of crystal grains is more favorably controlled, and the urea is matched with the hydrothermal reaction for hydrolysis, so that the growth of the crystal grains can be effectively controlled; the nickel cobalt lithium manganate ternary positive electrode material with the coating agent on the outer layer is coupled with the specially-conductive BP2000, so that the charge mass transfer resistance of the battery is reduced, the rapid movement of electrons is promoted, the electrochemical performance of the finally prepared coated nickel cobalt lithium manganate ternary positive electrode material is greatly improved, and a good synergistic effect is achieved.

Claims (11)

1. A preparation method of a coated nickel cobalt lithium manganate ternary positive electrode material comprises the following steps:
mixing nickel salt, cobalt salt and manganese salt, dissolving in water to form a homogeneous solution, and adding urea into the homogeneous solution to dissolve to obtain a mixed solution;
performing hydrothermal reaction on the mixed solution, filtering, washing and drying to obtain a nickel-cobalt-manganese precursor;
adding a lithium source into the nickel-cobalt-manganese precursor, uniformly mixing, heating at 300-;
mixing the nickel cobalt lithium manganate ternary positive electrode material with a coating agent, and sintering to obtain a nickel cobalt lithium manganate ternary positive electrode material with an outer layer containing the coating agent;
adding BP2000 into the nickel cobalt lithium manganate ternary positive electrode material of which the outer layer contains the coating agent for ball milling, thereby preparing the coated nickel cobalt lithium manganate ternary positive electrode material;
the mass of the lithium source is 1.03-1.11 times of that of the nickel-cobalt-manganese precursor;
the amount of the urea is 5-15 times of the total amount of the nickel salt, the cobalt salt and the manganese salt;
the mass of the coating agent is 0.1-0.5% of that of the nickel cobalt lithium manganate ternary positive electrode material;
the coating agent is aluminum fluoride;
the weight of the BP2000 is 0.1-2% of that of the nickel cobalt lithium manganate ternary positive electrode material with the coating agent on the outer layer.
2. The method of claim 1, wherein: the molar ratio of the nickel salt to the cobalt salt to the manganese salt is (3-8): (1-4): (1-3).
3. The method of claim 2, wherein: the nickel salt comprises one or more of nickel sulfate, nickel chloride, nickel acetate and nickel nitrate.
4. The method of claim 2, wherein: the cobalt salt comprises one or more of cobalt sulfate, cobalt chloride, cobalt acetate and cobalt nitrate.
5. The method of claim 2, wherein: the manganese salt comprises one or more of manganese sulfate, manganese chloride, manganese acetate and manganese nitrate.
6. The method of claim 1, wherein: the lithium source comprises one or a combination of lithium carbonate, lithium hydroxide, lithium acetate and lithium nitrate.
7. The method of claim 1, wherein: in the second step, the temperature for performing the hydrothermal reaction is 120-180 ℃; the reaction time is 8-24 h.
8. The method of claim 1, wherein: in the fourth step, the sintering temperature is 400-700 ℃; the sintering time is 3-6 h.
9. The method of claim 1, wherein: in the fifth step, a high-energy ball milling method is adopted for ball milling, and the ball-to-material ratio is 10: 1; the ball milling time is 100-; the stirring speed of the ball mill is 500-900 r/min.
10. A coated nickel cobalt lithium manganate ternary cathode material, which is prepared by the preparation method of any one of claims 1-9; the particle size of the coated nickel cobalt lithium manganate ternary cathode material is 8-12 mu m.
11. The coated nickel cobalt lithium manganate ternary cathode material of claim 10, in the field of lithium ion batteries.
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