CN111072074A - Preparation method of indium-doped nickel cobalt lithium manganate material - Google Patents

Preparation method of indium-doped nickel cobalt lithium manganate material Download PDF

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Publication number
CN111072074A
CN111072074A CN201911339639.1A CN201911339639A CN111072074A CN 111072074 A CN111072074 A CN 111072074A CN 201911339639 A CN201911339639 A CN 201911339639A CN 111072074 A CN111072074 A CN 111072074A
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Prior art keywords
indium
nickel cobalt
lithium manganate
cobalt lithium
doped nickel
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CN201911339639.1A
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Chinese (zh)
Inventor
崔大祥
卢玉英
张芳
阳靖峰
张道明
王亚坤
焦靖华
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a preparation method of an indium-doped nickel cobalt lithium manganate material, which comprises the steps of weighing raw materials according to a stoichiometric ratio, preparing a microemulsion, adding the raw materials into deionized water, uniformly stirring, adding the mixture into the microemulsion, carrying out ultrasonic dispersion, carrying out freeze drying on the solution, and sintering the treated raw materials to obtain the indium-doped nickel cobalt lithium manganate positive electrode material. In3+The material has electrochemical inertia, does not generate valence state change during charging and discharging, has no volume change, can play a role of a framework, and is beneficial to improving the cycle life and the safety performance of the material. The indium-doped nickel cobalt lithium manganate positive electrode material obtained by the method has higher gram capacity, improves the stability of the material and effectively delays the attenuation problem of the battery.

Description

Preparation method of indium-doped nickel cobalt lithium manganate material
Technical Field
The invention relates to a preparation method of a nickel cobalt lithium manganate material, in particular to a preparation method of an indium-doped nickel cobalt lithium manganate material.
Background
Lithium nickel cobalt manganese is one of the key materials of lithium ion batteries. Compared with other lithium ion battery anode materials such as lithium manganate and lithium iron phosphate, the lithium nickel cobalt manganese oxide material and the lithium cobaltate are very close to each other in electrochemical performance and processability, so that the lithium nickel cobalt manganese oxide material becomes a new battery material to gradually replace the lithium cobaltate, and becomes a favorite of a new generation of lithium ion battery material. However, pure nickel cobalt lithium manganate (LNCM) is charged and discharged
In the process, the collapse of the material structure is easily caused by the de-intercalation of Li ions and the change of the valence states of Ni, Co and Mn ions, and finally, the cycle life and the safety of the battery are greatly damaged. It is believed that Ni ions will generate Ni during charging voltages below 4.4V (vs Li +/Li)2+/3+To Ni4+And, with a contraction in volume, on continued charging to a higher voltage, Co3+Will participate in the reaction and transform into Co4+. If the charging voltage is too high and the charging depth is too large, the volume shrinkage of the material is irreversible, resulting in loss of electrochemical activity.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method of a nickel cobalt lithium manganate positive electrode material, so as to solve the problems of unstable crystal structure and poor cycle life of the existing nickel cobalt lithium manganate positive electrode material.
The purpose of the invention is realized by the following scheme: a preparation method of an indium-doped nickel cobalt lithium manganate positive electrode material comprises the following steps:
(1) in terms of LiNi0 .6Co0 .2Mn0 .2-xYbxO2Weighing water-soluble lithium source, nickel source, cobalt source, manganese source and indium source according to the stoichiometric ratio of (1): 0.6: 0.2: 0.2-x: x, wherein 0<x≤0.02；
(2) Mixing a cosurfactant and a cationic surfactant according to the mass ratio of 100 g: adding 3g of the mixture into a beaker, and performing electromagnetic stirring to obtain a uniformly mixed solution, wherein the cosurfactant is one or a combination of isoamyl alcohol, n-hexanol and n-pentanol;
(3) adding the raw materials weighed in the step (1) into deionized water, stirring uniformly, adding into the uniform solution in the step (2), and performing ultrasonic dispersion for 20-30 min;
(4) freezing the solution obtained in the step (3) at-80 ℃, and freeze-drying the frozen sample in a freeze dryer;
(5) and (5) sintering the raw materials treated in the step (4), wherein the sintering temperature is 700-1000 ℃, and the sintering time is 5-8 hours, so as to prepare the indium-doped nickel cobalt lithium manganate positive electrode material.
The cationic surfactant is one or the combination of hexadecyl trimethyl ammonium chloride, tetradecyl-dimethyl pyridine ammonium bromide and tridecyl methyl ammonium chloride.
In the step (4), the freeze drying condition is vacuum pumping, and the freeze drying time is 16-24 hours.
The invention provides a preparation method of an indium-doped nickel cobalt lithium manganate positive electrode material, and provides a preparation method which is simple in preparation process, strong in operability, easy to control the particle size of the material, large in specific surface area of the material and beneficial to improving the electrochemical performance of the material. Due to electrochemical inertness, In3+The doping does not participate in the reaction in the charge and discharge process of the material, does not generate the change of valence state, can be used as a framework to stabilize the crystal structure, thereby improving the cycle performance and the safety performance of the material. The indium-doped nickel cobalt lithium manganate positive electrode material obtained by the method has higher gram capacity, improves the stability of the material and effectively delays the attenuation problem of the battery.
Drawings
FIG. 1 is a graph showing the relationship between the cycle number and the capacity of button cells prepared from the material obtained in the example of the present invention.
Detailed Description
The present invention is described in detail below by way of specific examples, which are merely illustrative of the present invention, but the scope of the present invention is not limited to these examples.
Example 1:
an indium-doped nickel cobalt lithium manganate material is prepared by the following steps:
(1) weighing lithium sulfate, nickel sulfate, cobalt sulfate, manganese sulfate and indium oxide according to the stoichiometric ratio of Li1.01Ni0.6Co0.2Mn0.18Yb0.02, wherein the molar ratio of Li, Ni, Co, Mn and In is 1.01: 0.6: 0.2: 0.18: 0.02;
(2) n-amyl alcohol and hexadecyl trimethyl ammonium chloride according to the mass ratio of 100 g: adding 3g of the mixture into a beaker, and electromagnetically stirring to obtain a uniformly mixed solution;
(3) adding deionized water into the raw materials weighed in the step (1), stirring uniformly, adding into the uniform solution in the step (2), and performing ultrasonic dispersion for 20-30min to obtain a solution;
(4) freezing the solution obtained in the step (3) at-80 ℃, and freeze-drying the frozen sample in a freeze dryer for 24 hours to obtain a freeze-dried sample;
(5) and (4) sintering the freeze-dried sample obtained in the step (4), wherein the sintering temperature is 700 ℃, the sintering time is 8 hours, so that the indium-doped nickel cobalt lithium manganate positive electrode material is prepared, the cycle characteristics are shown in figure 1, and the capacity of 50 cycles and 5 cycles is basically the same.
Example 2:
an indium-doped nickel cobalt lithium manganate positive electrode material is similar to that in example 1, and is prepared by the following steps:
(1) weighing lithium sulfate, nickel sulfate, cobalt sulfate, manganese sulfate and indium oxide according to the stoichiometric ratio of Li1.01Ni0.6Co0.2Mn0.19Yb0.01, and enabling the molar ratio of Li, Ni, Co, Mn and In to be 1.01: 0.6: 0.2: 0.19: 0.01;
(2) mixing n-amyl alcohol and hexadecyl trimethyl ammonium chloride according to the mass ratio of 100 g: adding 3g of the mixture into a beaker, and electromagnetically stirring to obtain a uniformly mixed solution;
(3) adding deionized water into the raw materials weighed in the step (1), stirring uniformly, adding the mixture into the mixed solution prepared in the step (2), and performing ultrasonic dispersion for 20-30 min;
(4) putting the solution obtained in the step (3) into a freezing environment at the temperature of-80 ℃, and after freezing, putting the solution into a freeze dryer for freeze drying for 24 hours to obtain a freeze-dried sample;
(5) and sintering the freeze-dried sample at the sintering temperature of 1000 ℃ for 5 hours to obtain the indium-doped nickel cobalt lithium manganate material.
Example 3:
an indium-doped nickel cobalt lithium manganate positive electrode material is similar to that in example 1, and is prepared by the following steps:
(1) weighing lithium sulfate, nickel sulfate, cobalt sulfate, manganese sulfate and indium oxide according to the stoichiometric ratio of LiNi0.6Co0.2Mn0.18Yb0.02, wherein the molar ratio of Li, Ni, Co, Mn and In is 1.01: 0.6: 0.2: 0.18: 0.02;
(2) mixing n-amyl alcohol and hexadecyl trimethyl ammonium chloride according to the mass ratio of 100 g: adding 3g of the mixture into a beaker, and electromagnetically stirring to obtain a uniformly mixed solution;
(3) adding deionized water into the raw materials weighed in the step (1), stirring uniformly, adding the mixture into the mixed solution prepared in the step (2), and performing ultrasonic dispersion for 20-30 min;
(4) putting the solution obtained in the step (3) into a freezing environment at the temperature of-80 ℃, and after freezing, putting the solution into a freeze dryer for freeze drying for 16 hours to obtain a freeze-dried sample;
(5) and sintering the freeze-dried sample at 850 ℃ for 8 hours to obtain the indium-doped nickel cobalt lithium manganate material.

Claims (3)

1. The preparation method of the indium-doped nickel cobalt lithium manganate material is characterized by comprising the following steps of:
(1) in terms of LiNi0 .6Co0 .2Mn0 .2-xYbxO2Weighing water-soluble lithium source, nickel source, cobalt source, manganese source and indium source according to the stoichiometric ratio of (1): 0.6: 0.2: 0.2-x: x is the number ofWherein 0 is<x≤0.02；
(2) Mixing a cosurfactant and a cationic surfactant according to the mass ratio of 100 g: adding 3g of the mixture into a beaker, and performing electromagnetic stirring to obtain a uniformly mixed solution, wherein the cosurfactant is one or a combination of isoamyl alcohol, n-hexanol and n-pentanol;
(3) adding the raw materials weighed in the step (1) into deionized water, stirring uniformly, adding into the uniform solution in the step (2), and performing ultrasonic dispersion for 20-30min to obtain a solution;
(4) freezing the solution obtained in the step (3) at-80 ℃, and freeze-drying the frozen sample in a freeze dryer;
(5) and (5) sintering the raw materials treated in the step (4), wherein the sintering temperature is 700-1000 ℃, and the sintering time is 5-8 hours, so as to prepare the indium-doped nickel cobalt lithium manganate positive electrode material.
2. The preparation method of the indium-doped nickel cobalt lithium manganate positive electrode material according to claim 1, characterized in that: the cationic surfactant is one or the combination of hexadecyl trimethyl ammonium chloride, tetradecyl-dimethyl pyridine ammonium bromide and tridecyl methyl ammonium chloride.
3. The preparation method of the indium-doped nickel cobalt lithium manganate positive electrode material according to claim 1, characterized in that: in the step (4), the freeze drying condition is vacuum pumping, and the freeze drying time is 16-24 hours.
CN201911339639.1A 2019-12-23 2019-12-23 Preparation method of indium-doped nickel cobalt lithium manganate material Pending CN111072074A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101621125A (en) * 2009-02-13 2010-01-06 成都晶元新材料技术有限公司 Nickel-cobalt-manganese multi-doped lithium ion battery cathode material and preparation method thereof
CN102122715A (en) * 2011-01-25 2011-07-13 湖南汇通科技有限责任公司 Indium-doped lithium manganese, and preparation method and application thereof
CN106129381A (en) * 2016-08-31 2016-11-16 广西茗匠科技有限公司 All solid state lithium ion power battery anode material preparation method
CN106252593A (en) * 2016-08-31 2016-12-21 四川剑兴锂电池有限公司 A kind of anode material for lithium-ion batteries and preparation method thereof
CN107394175A (en) * 2017-07-31 2017-11-24 天津银隆新能源有限公司 Rear-earth-doped ternary material and preparation method thereof
CN110474026A (en) * 2019-07-03 2019-11-19 广东邦普循环科技有限公司 A kind of nickle cobalt lithium manganate tertiary cathode material and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101621125A (en) * 2009-02-13 2010-01-06 成都晶元新材料技术有限公司 Nickel-cobalt-manganese multi-doped lithium ion battery cathode material and preparation method thereof
CN102122715A (en) * 2011-01-25 2011-07-13 湖南汇通科技有限责任公司 Indium-doped lithium manganese, and preparation method and application thereof
CN106129381A (en) * 2016-08-31 2016-11-16 广西茗匠科技有限公司 All solid state lithium ion power battery anode material preparation method
CN106252593A (en) * 2016-08-31 2016-12-21 四川剑兴锂电池有限公司 A kind of anode material for lithium-ion batteries and preparation method thereof
CN107394175A (en) * 2017-07-31 2017-11-24 天津银隆新能源有限公司 Rear-earth-doped ternary material and preparation method thereof
CN110474026A (en) * 2019-07-03 2019-11-19 广东邦普循环科技有限公司 A kind of nickle cobalt lithium manganate tertiary cathode material and preparation method thereof

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Application publication date: 20200428