CN110563052A - preparation method of carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material - Google Patents

preparation method of carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material Download PDF

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CN110563052A
CN110563052A CN201910857786.1A CN201910857786A CN110563052A CN 110563052 A CN110563052 A CN 110563052A CN 201910857786 A CN201910857786 A CN 201910857786A CN 110563052 A CN110563052 A CN 110563052A
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positive electrode
lithium nickel
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nickel manganese
lanthanum
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魏爱佳
白薛
何蕊
李晓辉
牛庾鑫
张利辉
刘振法
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Energy Research Institute of Hebei Academy of Sciences
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Abstract

The invention discloses a preparation method of a carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material, and belongs to the technical field of modified lithium nickel manganese oxide positive electrode materials. The preparation method comprises the following steps: (1) weighing lithium carbonate, manganese dioxide and nickel oxide, adding ethanol or water, grinding, mixing, drying and sintering to obtain a lithium nickel manganese oxide positive electrode material; (2) preparing a sodium alginate solution and a metal lanthanum salt solution, adding the cathode material obtained in the step (1) into the sodium alginate solution, stirring, then dropwise adding the mixture into the metal lanthanum salt solution, after dropwise adding, performing suction filtration, washing, drying, and calcining in an inert gas to obtain the carbon and lanthanum oxide co-coated lithium nickel manganese oxide cathode material. After the positive electrode material obtained by the method is cycled for 200 times at the rate of 1C, the capacity retention rate at normal temperature can reach 93%, and the capacity retention rate at high temperature of 55 ℃ is 90%, so that the specific capacity and the cycling stability of the lithium nickel manganese oxide positive electrode material at normal temperature and high temperature are greatly improved.

Description

preparation method of carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material
Technical Field
The invention relates to the technical field of modified lithium nickel manganese oxide cathode materials.
Background
The lithium battery has the advantages of high working voltage, high energy density and power density, no memory effect, long cycle life, environmental friendliness, low self-discharge rate and the like. As one of batteries having excellent performance in commercial secondary power sources, lithium ion batteries are widely used in the fields of portable electronic products such as mobile phones, notebook computers, and cameras, and small and medium-sized transportation equipment such as electric bicycles. At present, in a lithium battery, a positive electrode material not only directly participates in an electrochemical reaction as an electrode material, but also is a main provider of lithium ions in the reaction, and the performance of the positive electrode material directly influences various characteristics and indexes of the battery, so that the positive electrode material is the core and the key of a lithium battery technology. One of the research hotspots of the current cathode material, high voltage spinel-type lithium nickel manganese oxide (LiNi)0.5Mn1.5O4) The method has the advantages of high discharge voltage, high energy density, excellent safety, relatively low cost and the like. The energy density of the lithium nickel manganese oxide reaches 650 Wh kg-1Significantly higher energy density than conventional materials, such as lithium cobaltate (518 Wh kg)-1) Lithium manganate (400 Wh kg)-1) Lithium iron phosphate (495 Wh kg)-1) And the lithium nickel manganese oxide anode material does not need atmosphere protection in the preparation process, can be directly sintered and synthesized in the air atmosphere, is very suitable for large-scale production, and has an electrodeGreat research value and application prospect.
However, due to limitations in power density and energy density, its application in large fields such as electric vehicles, hybrid electric vehicles, and smart grids has been problematic. The lithium nickel manganese oxide anode material has a 4.7V high-voltage platform, so that the material has the problems of poor rate performance, poor cycle performance and the like in the charging and discharging processes. The main reasons are: firstly, the structure of a lithium nickel manganese oxide material is damaged in the charging and discharging processes, so that lithium ions cannot be normally inserted back, and capacity attenuation is caused; secondly, the high voltage decomposes the electrolyte, the decomposition product reacts with the electrode material, the internal resistance is increased, the desorption of lithium ions is hindered, a lithium source is lost, the capacity is attenuated, and the cycle life is influenced, so that the key point for solving the problem is to modify the lithium nickel manganese oxide material and find the electrode material with high energy and power density.
The coating material in the prior art is mainly a single simple substance or compound, and includes a metal simple substance, a metal oxide, a phosphate or other inorganic substances, and the like.
CN109088062A discloses a preparation method of a polyimide-coated halogen element-doped modified lithium nickel manganese oxide material, wherein polyimide is adopted to carry out coating modification and halogen doping on a lithium nickel manganese oxide positive electrode material, the coating material is a single compound, and the polyimide has poor conductivity, so that a carbon material with good conductivity is adopted as a coating material and is coated with metal oxide lanthanum oxide together, so that a compact co-coating layer is formed, side reactions of electrolyte and the surface of an electrode material under a high voltage of 5V are effectively prevented, and the electrochemical performance of the material is further improved.
CN104347855A discloses a preparation method and application of phosphate-coated lithium nickel manganese oxide, firstly preparing a lithium nickel manganese oxide positive electrode material, and then coating and modifying the positive electrode material by using phosphate, but the single phosphate modification does not improve the power density and the energy density of the positive electrode material, and the coating of the phosphate increases the resistance between the material and an electrolyte, thereby hindering the insertion and the removal of lithium ions.
CN109888208A discloses a positive electrode material of lithium ion battery and its preparation method, the positive electrode material is lithium cobaltate, lithium nickel cobalt aluminate, lithium nickel cobalt manganese oxide, lithium iron phosphate, lithium nickel manganese oxide or lithium nickel cobalt oxide, and discloses three coating materials: the composite material is a lithium titanium composite oxide, a lithium zirconium composite oxide and/or a lithium phosphorus composite compound, but only one of the lithium titanium composite oxide, the lithium zirconium composite oxide and/or the lithium phosphorus composite compound is selected during coating, so that the modification effect is poor, and the specific capacity and the cycling stability performance at normal temperature and high temperature are poor.
Disclosure of Invention
The invention aims to provide a lithium nickel manganese oxide positive electrode material with excellent rate capability and cycling stability.
The method has the advantages that the method for realizing carbon and lanthanum oxide co-coating by using a one-step method is used for modifying the lithium nickel manganese oxide material, so that the conductivity of the material is improved, the corrosion of side reaction of electrolyte is inhibited, and the rate capability and the cycling stability of the material are effectively improved.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
The preparation method of the carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material comprises the following steps:
(1) Weighing lithium carbonate, manganese dioxide and nickel oxide, adding ethanol or water, grinding and mixing, drying and sintering the obtained mixture to obtain a lithium nickel manganese oxide positive electrode material;
(2) Preparing a sodium alginate solution and a metal lanthanum salt solution, adding the lithium nickel manganese oxide positive electrode material obtained in the step (1) into the sodium alginate solution, stirring, then dropwise adding the liquid phase mixture into the metal lanthanum salt solution, standing, filtering, washing after dropwise adding, drying the mixture, and calcining under inert gas to obtain the carbon and lanthanum oxide co-coated lithium nickel manganese oxide positive electrode material.
The molar ratio of the lithium carbonate to the nickel oxide to the manganese dioxide in the step (1) is =0.525:0.5:1.5, the molar ratio of the lithium carbonate to the nickel oxide to the manganese dioxide is converted into the molar ratio of the Li to the Ni to the Mn of 1.05:0.5:1.5, and the lithium nickel manganese oxide positive electrode material LiNi is obtained0.5Mn1.5O4。
the grinding and mixing in the step (1) is ball milling and mixing, wherein the ball milling rotating speed is 800 revolutions per minute, and the time is 1 ~ 3 hours.
the drying temperature in the step (1) is 105 +/-2 ℃.
pre ~ sintering at 500 ℃ for 3 ~ 5h in the step (1), and then sintering at 800 ℃ for 7 ~ 10 h.
the concentration of the sodium alginate solution in the step (2) is 1-3 wt.%.
In the step (2), the salt solution of the metal lanthanum is a salt solution of lanthanum nitrate, lanthanum chloride, lanthanum acetate or lanthanum sulfate, and the molar ratio of the metal lanthanum salt to the sodium alginate is 1.2: 1.
In the step (2), the mass ratio of the lithium nickel manganese oxide positive electrode material to the sodium alginate solution is 1: 1.
in the step (2), the calcining temperature is ~ 600 ℃, and the calcining time is 6 h.
The drying conditions in the step (2) are as follows: drying at 100 + -5 deg.C for 4 h.
The sodium alginate and various metal salt ions with different valence states can be complexed into microspheres, so that the sodium alginate can be widely applied to the fields of food, medicine, cosmetics, biotechnology and the like. In the experiment, sodium alginate and metal lanthanum ions are complexed to form microspheres wrapping the alginic acid ions and the metal lanthanum ions of the lithium nickel manganese oxide positive electrode material, and then the residual metal lanthanum ions and the displaced sodium ions are washed away by water, dried and calcined to obtain the modified lithium nickel manganese oxide positive electrode material which is coated by a layer of carbon and lanthanum oxide coating layer. It is well known that a large number of oxides and fluorides (Al)2O3、ZnO、Bi2O3、SnO2、AlF3、MgF2Etc.) are used for coating modified lithium nickel manganese oxide cathode materials, which are very helpful for improving the electrochemical performance of the materials, but the substances are coated on the surface of the lithium nickel manganese oxide, so that the electronic conductivity of the surface of the materials is reduced. Because the carbon material has good conductivity, the co-coating layer formed by using the means of co-coating lanthanum oxide and carbon can effectively prevent side reactions, improve the conductivity of the surface of the material, reduce the electrode impedance of the material and enable the modified lithium nickel manganese oxide material to have more excellent multiplying power and cycle stability.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
The method has the advantages that the method for realizing carbon and lanthanum oxide co-coating by using a one-step method is used for modifying the lithium nickel manganese oxide material, so that the conductivity of the material is improved, the corrosion of side reaction of electrolyte is inhibited, and the rate capability and the cycling stability of the material are effectively improved.
According to the method, the modified lithium manganate positive electrode material is coated by two substances, and after the modified lithium nickel manganese oxide positive electrode material is cycled for 200 times at a rate of 1C, the capacity retention rate at normal temperature can reach 93%, and the capacity retention rate at high temperature of 55 ℃ is 90%, so that the specific capacity and the cycling stability of the lithium nickel manganese oxide positive electrode material at normal temperature and high temperature are greatly improved.
According to the invention, a carbon material with good conductivity is used as a coating material and is coated with lanthanum oxide together, so that a compact co-coating layer is formed, side reaction of electrolyte and the surface of an electrode material under a high voltage of 5V is effectively prevented, and the electrochemical performance of the material is further improved.
drawings
FIG. 1 is a scanning electron microscope image of a carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide cathode material prepared in example 1 of the invention.
Fig. 2 is a cycle performance curve of the carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material prepared in example 1 at a rate of 1C, at a normal temperature of 25 ℃ and at a high temperature of 55 ℃.
Fig. 3 is a rate performance test curve of the carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide cathode material prepared in example 1 of the present invention.
Detailed Description
Example 1
The preparation method of the carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material comprises the following steps:
(1) Weighing 1.94g of lithium carbonate, 7.25g of manganese dioxide and 1.89g of nickel oxide in stoichiometric ratio, putting the materials into an 80mL ball milling tank, ball milling the materials at the rotating speed of 800 rpm for 2h by using 30mL of absolute ethyl alcohol as a solvent, putting the obtained mixture into an oven to dry the mixture at 105 ℃, presintering the mixture at 500 ℃ for 3h, and then sintering the mixture at 800 ℃ for 9h to obtain the pure-phase lithium nickel manganese oxide positive electrode material.
(2) Preparing 5g of sodium alginate solution with the concentration of 1 wt.%, adding 5g of the pure-phase lithium nickel manganese oxide positive electrode material obtained in the step (1) into the sodium alginate solution, adding 5mL of water for dilution, and uniformly stirring on a magnetic stirrer. And then 12.5 mL of lanthanum nitrate hexahydrate solution with the concentration of 1% is prepared, the mixed solution of the lithium nickel manganese oxide and the sodium alginate is placed on a sample injector and is dropwise added into the lanthanum nitrate solution at the dropping speed of 0.1mL/min, standing is carried out for 10h after the dropping is finished, suction filtration is carried out, deionized water is used for washing off redundant lanthanum nitrate solution and replaced sodium ions, drying is carried out for 4h at the temperature of 105 ℃, and calcining is carried out for 6h at the temperature of 400 ℃ under inert gas, so that the carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide anode material is obtained.
According to electrochemical tests, the obtained carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material has the first discharge specific capacity of 136.6mAh/g at the rate of 0.2C, after the material is cycled for 200 times at the rate of 1C, the specific capacity is 123.6 mAh/g, the capacity retention rate is 93%, and the capacity retention rate of the material is still kept at 90% after the material is cycled for 200 times at the rate of 1C at the high temperature of 55 ℃.
Example 2
The preparation method of the carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material comprises the following steps:
(1) Weighing 1.94g of lithium carbonate, 7.25g of manganese dioxide and 1.89g of nickel oxide in stoichiometric ratio, putting the materials into an 80mL ball milling tank, using 30mL of water as a solvent, carrying out ball milling at the rotating speed of 800 rpm for 3h, putting the obtained mixture into an oven, drying the mixture at 105 ℃, presintering the mixture at 500 ℃ for 4h, and sintering the mixture at 800 ℃ for 10h to obtain the pure-phase lithium nickel manganese oxide cathode material.
(2) preparing 5g of sodium alginate solution with the concentration of 2 wt.%, adding 5g of the pure-phase lithium nickel manganese oxide positive electrode material obtained in the step (1) into the sodium alginate solution, adding 5mL of water for dilution, and uniformly stirring on a magnetic stirrer. And then preparing 25 mL of lanthanum nitrate hexahydrate solution with the concentration of 1%, dropwise adding the mixed solution of the lithium nickel manganese oxide and sodium alginate on a sample injector at the dropping speed of 0.1mL/min, standing for 10h after the dropping, performing suction filtration, washing off redundant lanthanum nitrate solution and replaced sodium ions by deionized water, drying for 4h at 100 ℃, and calcining for 6h at 500 ℃ under inert gas to obtain the carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material.
according to electrochemical tests, the obtained carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material has the first discharge specific capacity of 134.5mAh/g at the rate of 0.2C, after the material is cycled for 200 times at the rate of 1C, the specific capacity is 122.1mAh/g, the capacity retention rate is 92%, and after the material is cycled for 200 times at the rate of 1C at the high temperature of 55 ℃, the capacity retention rate is 89.1%.
example 3
The preparation method of the carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material comprises the following steps:
(1) Weighing 1.94g of lithium carbonate, 7.25g of manganese dioxide and 1.89g of nickel oxide in stoichiometric ratio, putting the materials into an 80mL ball milling tank, ball milling the materials at the rotating speed of 800 rpm for 2h by taking 30mL of absolute ethyl alcohol as a solvent, putting the obtained mixture into an oven to dry the mixture at 103 ℃, presintering the mixture at 500 ℃ for 5h, and then sintering the mixture at 800 ℃ for 7h to obtain the pure-phase lithium nickel manganese oxide cathode material.
(2) preparing 5g of sodium alginate solution with the concentration of 3 wt.%, adding 5g of the pure-phase lithium nickel manganese oxide positive electrode material obtained in the step (1) into the sodium alginate solution, adding 5mL of water for dilution, and uniformly stirring on a magnetic stirrer. And then preparing 40 mL of 1% lanthanum nitrate solution, dropwise adding the mixed solution of the lithium nickel manganese oxide and sodium alginate into the lanthanum nitrate hexahydrate solution on a sample injector at the dropping speed of 0.1mL/min, standing for 10h after the dropping, performing suction filtration, washing off redundant lanthanum nitrate solution and replaced sodium ions by deionized water, drying for 4h at 105 ℃, and calcining for 6h at 600 ℃ under inert gas to obtain the carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material.
According to electrochemical tests, the obtained carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material has the first discharge specific capacity of 132.0mAh/g at the rate of 0.2C, after the material is cycled for 200 times at the rate of 1C, the specific capacity is 120 mAh/g, the capacity retention rate is 90.5%, and after the material is cycled for 200 times at the rate of 1C at the high temperature of 55 ℃, the capacity retention rate is 88%.
Example 4
The preparation method of the carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material comprises the following steps:
(1) Weighing 1.94g of lithium carbonate, 7.25g of manganese dioxide and 1.89g of nickel oxide in stoichiometric ratio, putting the materials into an 80mL ball milling tank, ball milling the materials at the rotating speed of 800 rpm for 2h by using 30mL of absolute ethyl alcohol as a solvent, putting the obtained mixture into an oven to dry the mixture at 105 ℃, presintering the mixture at 500 ℃ for 3h, and then sintering the mixture at 800 ℃ for 9h to obtain the pure-phase lithium nickel manganese oxide positive electrode material.
(2) Preparing 5g of sodium alginate solution with the concentration of 1 wt.%, adding 5g of the pure-phase lithium nickel manganese oxide positive electrode material obtained in the step (1) into the sodium alginate solution, adding 5mL of water for dilution, and uniformly stirring on a magnetic stirrer. And then preparing 7 mL of lanthanum chloride solution with the concentration of 1 wt.%, dropwise adding the mixed solution of the lithium nickel manganese oxide and sodium alginate into the lanthanum chloride solution on a sample injector at the dropping speed of 0.1mL/min, standing for 10h after the dropping, performing suction filtration, washing off the redundant lanthanum chloride solution by using deionized water, drying for 4h at 105 ℃, and calcining for 6h at 400 ℃ under inert gas to obtain the carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material.
According to electrochemical tests, the obtained carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material has the first discharge specific capacity of 135.3mAh/g at the rate of 0.2C, the specific capacity of 122.0 mAh/g and the capacity retention rate of 92.8% after the material is cycled for 200 times at the rate of 1C, and the capacity retention rate of the sample is 89% after the sample is cycled for 200 times at the rate of 1C at the high temperature of 55 ℃.
example 5
The preparation method of the carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material comprises the following steps:
(1) Weighing 1.94g of lithium carbonate, 7.25g of manganese dioxide and 1.89g of nickel oxide in stoichiometric ratio, putting the materials into an 80mL ball milling tank, ball milling the materials at the rotating speed of 800 rpm for 2h by using 30mL of absolute ethyl alcohol as a solvent, putting the obtained mixture into an oven to dry the mixture at 105 ℃, presintering the mixture at 500 ℃ for 3h, and then sintering the mixture at 800 ℃ for 9h to obtain the pure-phase lithium nickel manganese oxide positive electrode material.
(2) Preparing 5g of sodium alginate solution with the concentration of 2 wt.%, adding 5g of the pure-phase lithium nickel manganese oxide positive electrode material obtained in the step (1) into the sodium alginate solution, adding 5mL of water for dilution, and uniformly stirring on a magnetic stirrer. And then preparing 18 mL of lanthanum acetate solution with the concentration of 1 wt.%, dropwise adding the mixed solution of the lithium nickel manganese oxide and sodium alginate into the lanthanum acetate solution on a sample injector at the dropwise adding speed of 0.1mL/min, standing for 10h after dropwise adding, performing suction filtration, washing off redundant lanthanum acetate solution and replaced sodium ions by deionized water, drying for 4h at 105 ℃, and calcining for 6h at 500 ℃ under inert gas to obtain the carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material.
According to electrochemical tests, the obtained carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material has the first discharge specific capacity of 134.9mAh/g at the rate of 0.2C, after the material is cycled for 200 times at the rate of 1C, the specific capacity is 121.6 mAh/g, the capacity retention rate is 92.1%, and after the sample is cycled for 200 times at the rate of 1C at the high temperature of 55 ℃, the capacity retention rate is 90.5%.

Claims (10)

1. The preparation method of the carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material is characterized by comprising the following steps of: the method comprises the following steps:
(1) Weighing lithium carbonate, manganese dioxide and nickel oxide, adding ethanol or water, grinding and mixing, drying and sintering the obtained mixture to obtain a lithium nickel manganese oxide positive electrode material;
(2) Preparing a sodium alginate solution and a metal lanthanum salt solution, adding the lithium nickel manganese oxide positive electrode material obtained in the step (1) into the sodium alginate solution, stirring, then dropwise adding the liquid phase mixture into the metal lanthanum salt solution, standing, filtering, washing, drying and calcining under inert gas to obtain the carbon and lanthanum oxide co-coated lithium nickel manganese oxide positive electrode material.
2. The preparation method of the carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material according to claim 1, characterized in that: the molar ratio of the lithium carbonate to the nickel oxide to the manganese dioxide in the step (1) is =0.525:0.5:1.5, and the lithium nickel manganese oxide positive electrode is obtainedLiNi material0.5Mn1.5O4。
3. the preparation method of the carbon and lanthanum oxide co ~ coated modified lithium nickel manganese oxide positive electrode material according to claim 1, wherein the grinding and mixing in the step (1) is ball milling and mixing, the ball milling rotation speed is 800 revolutions per minute, and the time is 1 ~ 3 hours.
4. The preparation method of the carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material according to claim 1, characterized in that: the drying temperature in the step (1) is 105 +/-2 ℃.
5. the preparation method of the carbon and lanthanum oxide co ~ coated modified lithium nickel manganese oxide positive electrode material as claimed in claim 1, wherein in the step (1), the pre ~ sintering is carried out at 500 ℃ for 3 ~ 5h, and then the sintering is carried out at 800 ℃ for 7 ~ 10 h.
6. the preparation method of the carbon and lanthanum oxide co ~ coated modified lithium nickel manganese oxide positive electrode material as claimed in claim 1, wherein the concentration of the sodium alginate solution in the step (2) is 1 ~ 3 wt.%.
7. The preparation method of the carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material according to claim 6, characterized in that: the metal lanthanum salt solution in the step (2) is a solution of lanthanum nitrate, lanthanum chloride, lanthanum acetate or lanthanum sulfate, and the molar ratio of the metal lanthanum salt to the sodium alginate is 1.2: 1.
8. The preparation method of the carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material according to claim 1, characterized in that: the mass ratio of the lithium nickel manganese oxide positive electrode material to the sodium alginate solution in the step (2) is 1: 1.
9. the preparation method of the carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material as claimed in claim 1, wherein the calcination temperature in the step (2) is 400-600 ℃, and the calcination time is 6 h.
10. The preparation method of the carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material according to claim 1, characterized in that: the drying conditions in the step (2) are as follows: drying at 100 + -5 deg.C for 4 h.
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