CN110931775A - Modification method of lithium-rich manganese-based positive electrode material - Google Patents

Modification method of lithium-rich manganese-based positive electrode material Download PDF

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Publication number
CN110931775A
CN110931775A CN201911314045.5A CN201911314045A CN110931775A CN 110931775 A CN110931775 A CN 110931775A CN 201911314045 A CN201911314045 A CN 201911314045A CN 110931775 A CN110931775 A CN 110931775A
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lithium
positive electrode
rich manganese
electrode material
based positive
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吕晓霞
刘振
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Haian Changzhou University High-Tech R & D Center
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Haian Changzhou University High-Tech R & D Center
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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

A modification method of a lithium-rich manganese-based anode material belongs to the technical field of production of anode materials of lithium ion batteries. Putting the lithium-rich manganese-based positive electrode material into acid steam for fumigation, washing, drying and calcining the fumigated lithium-rich manganese-based positive electrode material to obtain a modified lithium-rich manganese-based positive electrode material; the structural formula of the lithium-rich manganese-based positive electrode material is as follows: xLi2MnO3·(1‑x)LiMO2According to the invention, through a simple process flow, the acid vapor is adopted to form an acid atmosphere to carry out acid treatment on the lithium-rich manganese-based positive electrode material, compared with acid leaching treatment, the acid treatment is mild, the damage of an acid solution to the surface of the material can be effectively avoided, the first irreversible capacity of the material is improved, and the cycle performance of the modified material is improved, so that the performance of the lithium-rich manganese-based positive electrode material is better improved.

Description

Modification method of lithium-rich manganese-based positive electrode material
Technical Field
The invention belongs to the technical field of production of lithium ion battery anode materials.
Background
The lithium ion battery as an efficient energy storage device can convert the electric energy into chemical energy for various fields. In recent years, based on the demand for higher specification energy storage devices in the field of new energy electric vehicles, development of lithium ion batteries in the directions of high specific energy, high power density, high safety, long cycle life, low cost and the like is urgent. Wherein the properties of the positive electrode material will directly influenceThe charge and discharge capacity, the cycle performance, the rate performance and the high-temperature thermal stability of the battery. The lithium-rich manganese-based anode material has high specific capacity and synthesizes LiCoO2、LiMnO2And LiNiO2The three advantages have higher specific capacity and working voltage, and quickly become the research focus in the field of energy and materials.
The lithium-rich manganese-based cathode material is considered to be one of the most promising cathode materials for breaking through the application bottleneck of the lithium ion battery at present due to the characteristics of low cost, good safety, high energy density and the like. However, the lithium-rich manganese-based positive electrode material itself has some serious problems, such as poor cycle performance, too fast voltage attenuation, too high first irreversible capacity, and the like, which seriously hinders the progress of commercial application thereof.
Disclosure of Invention
Aiming at the problems of the lithium-rich manganese-based positive electrode material, the invention provides a method for modifying the lithium-rich manganese-based positive electrode material by acid vapor treatment.
The technical scheme of the invention is as follows: putting the lithium-rich manganese-based positive electrode material into acid steam for fumigation, washing, drying and calcining the fumigated lithium-rich manganese-based positive electrode material to obtain a modified lithium-rich manganese-based positive electrode material; the structural formula of the lithium-rich manganese-based positive electrode material is as follows: xLi2MnO3·(1-x)LiMO2Wherein M is composed of Ni, Co and Mn, and x is more than 0 and less than 1.
The acid treatment of the invention by fumigation in acid vapour has two important processes, first H+/Li+The exchange reaction improves the oxidation-reduction capability of the material and accelerates the formation of a lithium channel; secondly, Li which is rich in lithium manganese base anode material can be filtered2MnO3Li of the composition2O, to form MnO2And MnO of2Lithium can be inserted in the discharging process, so that the insertion amount of Li is increased, and the performance of the material is improved.
Acid treatment has been studied in which the material is subjected to acid leaching, which causes a certain degree of corrosion of the surface of the material, and although it can reduce the loss of capacity, it has an adverse effect on its cycle performance.
The method has the advantages that through a simple process flow, the acid vapor is adopted to form an acid atmosphere to carry out acid treatment on the lithium-rich manganese-based positive electrode material, compared with acid leaching treatment, the acid treatment is mild, the damage of an acid solution to the surface of the material can be effectively avoided, the first irreversible capacity of the material is improved, and meanwhile, the cycle performance of the modified material is improved, so that the performance of the lithium-rich manganese-based positive electrode material is better improved.
Further, the acid is at least one of a hydrochloric acid aqueous solution with a concentration of 1-5 mol/L, a nitric acid aqueous solution with a concentration of 1-5 mol/L, an oxalic acid aqueous solution with a concentration of 1-5 mol/L and an acetic acid aqueous solution with a concentration of 1-5 mol/L. Acid steam treatment surface treatment of materials mainly by acidic atmosphere, which is mainly by H in acidic atmosphere+With the material surface Li+Carrying out H+/Li+Exchange reaction to make Li remained on the surface of the lithium-rich manganese-based cathode material2And O is removed, and a trace amount of spinel surface layers doped with Ni and Co can be formed on the surfaces of the lithium-rich material particles, so that the side reaction between the electrode and the electrolyte is inhibited, and the electrochemical performance of the material is improved. The surface treatment can be carried out on the material in a proper acid steam atmosphere within the concentration range of 1-5 mol/L.
The fumigating time is 5-24 hours. The acid vapor treatment method is mild, and the lithium-rich manganese-based cathode material needs to be treated in the acid atmosphere for enough time to carry out H+/Li+The exchange reaction is more sufficient in this time range. More preferably the time of fumigation is 12 hours.
In order to completely remove the moisture left in the positive electrode material due to the acid vapor treatment, the temperature environment for calcination was 300 ℃ and the calcination time was 3 hours.
Drawings
Fig. 1a is an SEM image of a positive electrode material without acid treatment.
FIG. 1b is an SEM image of modified material sample 1 taken after acetic acid vapor treatment.
FIG. 1c is an SEM image of modified material sample 2 taken after hydrochloric acid vapor treatment.
Fig. 2 is a first charge-discharge curve diagram of each sample of the positive electrode material.
Fig. 3 is a graph of cycle performance of each sample of positive electrode material.
Detailed Description
Firstly, preparing a lithium-rich manganese-based positive electrode material:
preparing a lithium-rich manganese-based precursor by adopting a coprecipitation method, preparing a metal salt solution by using sulfate, using sodium carbonate as a precipitator and using ammonia water as a complexing agent, controlling the sample injection speed to be 2-30 ml/min and the pH value to be 7-10, and carrying out coprecipitation reaction under the heating of a water bath at 60 ℃ to obtain a lithium-rich manganese-based precursor suspension. And settling, washing and drying to obtain the lithium-rich manganese-based precursor.
Uniformly mixing the prepared lithium-rich manganese-based precursor with lithium salt, calcining, heating to 500 ℃, preserving heat for 3 hours, heating to 900 ℃, preserving heat for 8 hours, and finally cooling to room temperature to obtain the lithium-rich manganese-based cathode material with a chemical formula of 0.5Li2MnO3·0.5Li（Ni1/3Co1/3Mn1/3）O2。
Secondly, a modification process:
implementing one step:
a certain amount of acetic acid is measured and added with deionized water for dilution, and then an acetic acid aqueous solution with the concentration of 2mol/L is obtained. Pouring the acetic acid aqueous solution into a container, hanging funnel-shaped filter paper at the bottleneck of the container, uniformly distributing the prepared lithium-rich manganese-based anode material on the filter paper, and covering a glass sheet at the upper opening of the filter paper to prevent acid vapor from escaping or liquefying and dropping into the material.
And then placing the container in a constant-temperature water bath at 40-60 ℃, and magnetically stirring the acetic acid aqueous solution in the container to form acid steam. Samples were taken after 12h of fumigation.
And washing each sample for 2-3 times by using deionized water, carrying out suction filtration, and then placing the well-filtered sample in an electrothermal blowing drying oven for drying for 2 hours at 70 ℃ to obtain a dried material. The dried material was calcined in a muffle furnace at 300 ℃ for 3h to remove moisture left in the material and to obtain modified material sample 1.
The second implementation:
a certain amount of hydrochloric acid is measured and added with deionized water for dilution, and then the hydrochloric acid aqueous solution with the concentration of 2mol/L is obtained. Pouring the hydrochloric acid aqueous solution into a container, hanging funnel-shaped filter paper at the bottleneck of the container, uniformly distributing the prepared lithium-rich manganese-based anode material on the filter paper, and covering a glass sheet at the upper opening of the filter paper to prevent acid vapor from escaping or liquefying and dropping into the material.
And then placing the container in a constant-temperature water bath at 40-60 ℃, and magnetically stirring the hydrochloric acid aqueous solution in the container to form acid steam. Samples were taken after 12h of fumigation.
And washing each sample for 2-3 times by using deionized water, carrying out suction filtration, and then placing the well-filtered sample in an electrothermal blowing drying oven for drying for 2 hours at 70 ℃ to obtain a dried material. The dried material was calcined in a muffle furnace at 300 ℃ for 3h to remove moisture left in the material and to obtain modified material sample 2.
Comparative example:
the prepared lithium-rich manganese-based positive electrode material is directly placed in an electric heating forced air drying oven to be dried for 2 hours at 70 ℃ without acid treatment, and the dried material is obtained. The dried material was calcined in a muffle furnace at 300 ℃ for 3h to remove moisture left by the material, resulting in sample 3 of material that was not acid treated.
Fourthly, assembling a battery:
and performing parallel test on the charge and discharge performance of each material sample by assembling a button cell.
Mixing each sample with binder and electric conduction at a mass ratio of 8: 1, adding appropriate amount of 1-methyl-2-pyrrolidone dropwise to obtain corresponding slurry, and uniformly coating the slurry on aluminum foil to obtain a mixture with a thickness of about 5mg/cm3After being respectively put into an oven for drying, the punching sheet forms three different anodes.
Lithium sheets were used as cathodes, respectively, and three different batteries were assembled in a glove box filled with argon gas.
Fifthly, analyzing the battery performance:
1. SEM analysis:
as can be seen from fig. 1a, 1b and 1 c: the shapes of the three material samples are spherical particles, and the surfaces of the materials treated by acetic acid are smoother, but the surfaces of the materials treated by hydrochloric acid are rougher.
2. And (3) electrochemical performance testing:
the modified material sample 1, the modified material sample 2 and the material sample 3 which is not treated by acid and obtained by the method are respectively assembled to form a battery, the first charge and discharge performance of the material is tested at 0.05 ℃, and the cycle performance is tested at 0.5 ℃.
As can be seen from FIG. 2, the comparative example material without acid treatment has a first discharge capacity of 268mAh/g and a charge-discharge efficiency of 73%; the first discharge capacities of the acetic acid vapor treatment material and the hydrochloric acid vapor treatment material in the first and second embodiments were 278Ah/g and 298Ah/g, respectively, and the charge and discharge efficiencies were 76% and 80% respectively. The material without acid treatment has obviously lower first discharge efficiency than the material treated by acid, so the acid treatment can improve the first charge-discharge efficiency of the material.
As can be seen from FIG. 3, the material subjected to hydrochloric acid vapor treatment in the second step has a higher first charge-discharge capacity but a lower cycle performance, and the cycle capacity decreases faster in the first 100 cycles and then tends to be smooth. The material subjected to acetic acid steam treatment has a more gentle circulation curve, and after 200 times of circulation, the capacity can be basically stabilized at about 150mAh/g, the capacity retention rate can reach about 80%, and the capacity retention rate is improved by about 10% compared with that of the untreated material of a comparative example.
Therefore, the acid steam treatment can improve the cycle performance of the material.

Claims (5)

1. A modification method of a lithium-rich manganese-based positive electrode material is characterized by comprising the following steps: putting the lithium-rich manganese-based positive electrode material into acid steam for fumigation, washing, drying and calcining the fumigated lithium-rich manganese-based positive electrode material to obtain a modified lithium-rich manganese-based positive electrode material; the structural formula of the lithium-rich manganese-based positive electrode material is as follows: xLi2MnO3·(1-x)LiMO2Wherein M is composed of Ni, Co and Mn, and x is more than 0 and less than 1.
2. The method for modifying a lithium-rich manganese-based positive electrode material according to claim 1, wherein the acid is at least one of a hydrochloric acid aqueous solution having a concentration of 1 to 2mol/L, a nitric acid aqueous solution having a concentration of 1 to 2mol/L, an oxalic acid aqueous solution having a concentration of 1 to 2mol/L, and an acetic acid aqueous solution having a concentration of 1 to 2 mol/L.
3. The method for modifying the lithium-rich manganese-based positive electrode material according to claim 1, wherein the time of the fumigation is 5 to 24 hours.
4. The method for modifying a lithium-rich manganese-based positive electrode material according to claim 3, wherein the time of the fumigation is 12 hours.
5. The method for modifying a lithium-rich manganese-based positive electrode material according to claim 1, 2, 3 or 4, characterized in that the calcination temperature environment is 300 ℃ and the calcination time is 3 h.
CN201911314045.5A 2019-12-19 2019-12-19 Modification method of lithium-rich manganese-based positive electrode material Pending CN110931775A (en)

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Cited By (7)

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Publication number Priority date Publication date Assignee Title
CN111509224A (en) * 2020-04-17 2020-08-07 中南大学 Linked modified lithium-rich manganese-based cathode material and preparation method thereof
CN111799468A (en) * 2020-08-13 2020-10-20 中南大学 Lithium ion battery anode material jointly modified by ionic conductor and heterostructure, preparation method and application
CN112038615A (en) * 2020-10-13 2020-12-04 昆山宝创新能源科技有限公司 Lithium-rich manganese-based composite cathode material and preparation method and application thereof
CN112216830A (en) * 2020-10-13 2021-01-12 厦门大学 Layered positive electrode material improved by organic acid and preparation method
CN112290009A (en) * 2020-10-30 2021-01-29 清华大学深圳国际研究生院 Manganese-based lithium-rich oxide cathode material, preparation method thereof and electrochemical device using manganese-based lithium-rich oxide cathode material
CN114242998A (en) * 2021-11-27 2022-03-25 桂林理工大学 Method for improving electrochemical performance of lithium-rich manganese-based oxide positive electrode material
CN115050959A (en) * 2022-05-31 2022-09-13 四川大学 Method for regulating and controlling surface interface of lithium-rich manganese-based positive electrode material by oxalic acid

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111509224A (en) * 2020-04-17 2020-08-07 中南大学 Linked modified lithium-rich manganese-based cathode material and preparation method thereof
CN111799468A (en) * 2020-08-13 2020-10-20 中南大学 Lithium ion battery anode material jointly modified by ionic conductor and heterostructure, preparation method and application
CN112038615A (en) * 2020-10-13 2020-12-04 昆山宝创新能源科技有限公司 Lithium-rich manganese-based composite cathode material and preparation method and application thereof
CN112216830A (en) * 2020-10-13 2021-01-12 厦门大学 Layered positive electrode material improved by organic acid and preparation method
CN112290009A (en) * 2020-10-30 2021-01-29 清华大学深圳国际研究生院 Manganese-based lithium-rich oxide cathode material, preparation method thereof and electrochemical device using manganese-based lithium-rich oxide cathode material
CN114242998A (en) * 2021-11-27 2022-03-25 桂林理工大学 Method for improving electrochemical performance of lithium-rich manganese-based oxide positive electrode material
CN115050959A (en) * 2022-05-31 2022-09-13 四川大学 Method for regulating and controlling surface interface of lithium-rich manganese-based positive electrode material by oxalic acid
CN115050959B (en) * 2022-05-31 2024-01-30 四川大学 Method for regulating and controlling surface interface of lithium-rich manganese-based positive electrode material by oxalic acid

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Application publication date: 20200327