CN111056578A - Method for modifying lithium-rich manganese-based positive electrode material - Google Patents

Method for modifying lithium-rich manganese-based positive electrode material Download PDF

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CN111056578A
CN111056578A CN201911201192.1A CN201911201192A CN111056578A CN 111056578 A CN111056578 A CN 111056578A CN 201911201192 A CN201911201192 A CN 201911201192A CN 111056578 A CN111056578 A CN 111056578A
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lithium
positive electrode
electrode material
rich manganese
based positive
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武建飞
宋德朋
牛全海
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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    • 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
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    • 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
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • 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
    • H01M4/624—Electric conductive fillers
    • 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
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Abstract

The invention discloses a lithium-rich manganese-based positive electrode material and a modification method thereof, and relates to the technical field of synthesis of positive electrode materials of lithium ion batteries. According to the invention, the precursor of the lithium-rich manganese-based anode material synthesized by a coprecipitation method is modified by element blending and doping, the anode material is coated and modified by a conductive polymer, and the modified lithium-rich manganese-based anode material is obtained by a multiple mixing modification method. The modified lithium-rich manganese-based positive electrode material is used for a lithium ion battery, so that the first charge-discharge coulombic efficiency of the lithium battery is obviously improved, and the cycle performance and the rate performance are obviously improved.

Description

Method for modifying lithium-rich manganese-based positive electrode material
Technical Field
The invention relates to the technical field of synthesis of lithium ion battery anode materials, in particular to a modification technology for preparation of a lithium-rich manganese-based anode material.
Background
With the vigorous development in the fields of electronic industry, energy storage power stations and the like, the problems of short endurance mileage and insufficient safety of electric automobiles are increasingly highlighted, and urgent needs are provided for the improvement of the energy density of lithium ion batteries. The low energy density of the lithium ion battery limits the endurance mileage of the electric automobile, so that the rapid development and the comprehensive popularization of the electric automobile are limited to a great extent, and people begin to put higher requirements on the energy density, the power density and the cycle life of the next generation of high-performance lithium ion battery. In order to satisfy the larger-scale application of electric vehicles, increasing the energy density is the ultimate issue of lithium ion battery research. With respect to the current industry technologies, the technology of increasing the energy density of lithium ion power batteries by reducing the mass of inactive substances in battery cells has been in the top, and the use of a cathode material with higher energy density to increase the energy density is a comparatively more effective method. With the increasing demand of the current society development for high specific energy battery systems, positive electrode materials with high potential and high specific capacity are becoming research hotspots in the field of energy storage.
Among the known cathode materials, the lithium-rich manganese-based cathode material can provide a reversible specific capacity of more than 250mAhg < -1 > and even 300mAhg < -1 > because more active lithium ions can participate in a lithium removal-insertion process in the charging and discharging processes, and is incomparable with cathode materials such as lithium cobaltate, lithium iron phosphate, ternary materials and the like which are already commercially applied at present, so that a great energy density improvement is brought to the lithium ion power battery. Meanwhile, the lithium-rich manganese-based positive electrode material mainly contains a cheaper manganese element, has low precious metal content, and has the advantages of low cost and good safety compared with common lithium cobaltate, manganese nickelate, ternary positive electrode materials and the like. Therefore, the lithium-rich manganese-based cathode material is very suitable for the cathode material of the new generation of high energy density lithium ion power battery, and is considered to be one of the most promising materials of the high energy density lithium ion power battery.
Although the lithium-rich manganese-based positive electrode material has high discharge specific capacity, the irreversible capacity loss of the lithium-rich manganese-based positive electrode material in the first cycle process is serious; high voltage activation is needed in the charging and discharging process, but the main structure of the material can be damaged in the process, the layered structure is converted into the spinel structure, active oxygen is released, the voltage platform is continuously reduced in the circulating process, and the capacity is continuously attenuated. In addition, the oxidative decomposition of the electrolyte in the circulation process can cause side reaction between the active material and the electrolyte, and further the circulation performance and the rate capability of the material are influenced. In the current research situation, the lithium-rich manganese-based positive electrode material has the technical problems of low coulombic efficiency, poor rate capability and cycle performance, rapid specific capacity attenuation and continuous voltage platform attenuation in the cycle process for the first time, which not only causes the reduction of the specific energy of the power battery, but also influences the normal operation of a battery management system and reduces the superiority brought by the high specific capacity to a certain extent. The fast specific capacity attenuation and the continuous discharge voltage attenuation in the circulating process are the most troublesome problems, and the large-scale application of the lithium-rich manganese-based cathode material in commerce is seriously hindered.
After ten years of efforts, the problem of specific capacity attenuation is well improved by means of surface modification and the like; in contrast, the problem of discharge voltage degradation is more intrinsic and needs to be improved. In many reports, the capacity of the modified and modified materials can be almost kept unchanged, but the working voltage is still continuously reduced. Therefore, the problem of voltage drop and poor cyclability is considered to be the root cause of the decrease in the energy density of the lithium-rich manganese-based positive electrode material battery, and is the most difficult problem to solve.
The surface modification treatment is considered to be the most effective method for improving the electrochemical performance of the lithium-rich manganese-based positive electrode material, and mainly comprises the following steps: element doping modification, surface coating modification, acid treatment modification, electronic structure regulation and control modification, development of a novel activation process and the like. After the lithium-rich manganese-based positive electrode material is modified, the problems of irreversible capacity, cycle performance, rate performance and voltage attenuation can be improved to a certain extent for the first time. However, these methods can only improve the performance of the material in some single aspect, and usually, the modification technology is complex and difficult to be fully used in commercial production. The development of modification technology which is easy to operate, low in cost and comprehensive in function is sought, and basic research and industrial development are seamlessly connected, so that the leapfrog development of the lithium-rich manganese-based positive electrode material is urgent.
Although the traditional surface coating material can improve the cycle performance of the lithium-rich cathode material, the reversible capacity and the rate performance are reduced. For example, MnO2 is used for carrying out surface coating modification on the lithium-rich cathode material, although the first irreversible capacity loss of the material is reduced and the cycle performance of the material at a high rate is improved, the discharge capacity of the modified material is relatively low. The oxide or phosphate of Al, Ce, Ru, Y and other elements is used as a coating layer, so that the first coulombic efficiency can be improved, and the rate capability and the cycle performance are improved.
The patent publication No. 109473660A modifies the lithium-rich manganese-based positive electrode material by adding ammonia water in the middle of the reaction, the method is different from the traditional method in the synthesis method, the surface modification treatment is not involved, and the appearance of the material is in a flower cluster shape, which is not beneficial to the subsequent further modification. Patent publication No. 109585833a surface-coated-modifies the positive electrode material by a spinel structure, but the spinel structure layer on the surface is not favorable for ion and electron transport. And these coating methods are too simple.
Disclosure of Invention
On the basis of the lithium-rich manganese-based anode material, Na/F elements are used for blending and doping, so that the structural stability of the material can be effectively improved; the surface of the battery is further coated by PEDOT and PSS conductive polymers, and the lithium-rich cathode material is modified by a surface multiple hybrid modification method, so that the electrochemical performance of the battery is greatly improved, and the structural stability, the coulombic efficiency, the cycle performance and the rate capability are improved.
The invention provides a method for modifying a lithium-rich manganese-based positive electrode material.
1. The lithium-rich manganese-based positive electrode material precursor is synthesized by adopting a coprecipitation method: dissolving Ni, Co and Mn sulfates in a certain amount in deionized water under stirring, continuously adding into a reaction kettle containing ammonium bicarbonate solution at a certain speed by a peristaltic pump, and adding Na2CO3Dropping the mixed solution with ammonia water into the reaction kettle at a certain speed, adjusting the pH environment value in the reaction kettle by controlling the dropping speed of the mixed solution and the ammonia water, carrying out coprecipitation reaction, and carrying out suction filtration, washing and drying on the obtained reaction solution after the reaction is finished to prepare a solid precursor;
2. uniformly mixing the obtained precursor material with lithium salt, a sodium source and a fluorine source, calcining, heating to 500 ℃ at the speed of 3 ℃ per minute, preserving heat for 5 hours, and then heating to 900 ℃ at the speed of 4 ℃ per minute, and calcining for 12 hours to obtain the lithium-rich manganese-based positive electrode material;
3. mixing the obtained positive electrode material with a conductive polymer poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) -PEDOT (PSS) in a dispersion liquid again, heating, stirring, filtering and drying to obtain a multi-mixing modified lithium-rich manganese-based positive electrode material;
4. the modified lithium-rich manganese-based positive electrode material is used for preparing a lithium ion battery pole piece, and PEDOT (Poly ethylene glycol Ether-butyl ether)/PSS (Polybutylece ether) is used as a conductive agent.
Compared with the prior art, the invention has the following advantages:
1. ammonium bicarbonate is added in the process of precursor synthesis, so that the generation of crystal clusters can be effectively inhibited, and a spherical precursor material with better appearance is obtained;
2. and the enhanced synergistic effect of each element is fully exerted by blending and doping the anions and the cations. Na with large ionic radius is beneficial to stabilizing the structure and inhibiting the transformation of the layered structure to the spinel structure, and compared with transition metal elements such as Nb/Zr and the like, the Na element has rich sources and low price; f doping is beneficial to balancing the energy of lithium ion insertion and extraction, and the structural stability and the cycle performance are improved;
3. conducting surface coating by using conductive polymer poly (3, 4-ethylenedioxythiophene) -poly (styrene sulfonic acid) (PEDOT: PSS) to provide a protective layer for the anode material. The PEDOT polymer can protect the anode material from the corrosion of the battery electrolyte, and can ensure the necessary lithium ion and electron transmission while preventing the chemical reaction between the battery and the electrolyte; and also prevents the conversion of the positive electrode material into a spinel structure, preventing the release of oxygen. Besides, the PEDOT coating can prevent lithium dendrite from generating to a great extent, so that the structure of the material is more stable in the circulating process, and the safety is improved. PEDOT coatings play multiple protective roles.
Drawings
Fig. 1 is an SEM image of the precursor materials obtained in examples 1 and 2 of the present invention.
Fig. 2 is a graph comparing the first charge and discharge curves of the lithium-rich positive electrode materials obtained in example 1 and example 2.
FIG. 3 is a graph comparing the cycle performance curves of the materials obtained in example 1 and example 2 of the present invention.
FIG. 4 is a graph comparing rate performance curves of materials obtained in example 1 and example 2 of the present invention.
Detailed Description
The present invention is further described below with reference to examples 1 and 2, but the following description is only for the purpose of explaining the present invention and does not limit the contents thereof.
Example 1: the method for modifying the lithium-rich manganese-based positive electrode material is prepared according to the following steps:
1) dissolving nickel sulfate, manganese sulfate and cobalt sulfate metal salt in a certain metering ratio in a certain amount of deionized water, continuously adding into a reaction kettle added with ammonium bicarbonate solution at a certain speed by using a peristaltic pump, and simultaneously adding Na2CO3Dropping the mixed solution with ammonia water into the reaction kettle at a certain speed, adjusting the pH environment value in the reaction kettle by controlling the dropping speed of the mixed solution and the ammonia water, carrying out coprecipitation reaction, and carrying out suction filtration, washing and drying on the obtained reaction solution after the reaction is finished to prepare a precursor of the lithium-rich manganese-based positive electrode material;
2) mixing Li2CO3Grinding and mixing the precursor, sodium carbonate and lithium fluoride according to a metered molar ratio, and calcining at high temperature in a muffle furnace in an air atmosphere after uniformly mixing; the calcination process adopts stage temperature control, the temperature is slowly raised to 500 ℃ and kept for 5h, then the temperature is slowly raised to 900 ℃ and calcined for 12h, and the material is cooled at room temperature after the calcination is finished, so as to obtain the doped modified lithium-rich manganese-based positive electrode material;
3) mixing and dispersing the doped modified lithium-rich manganese-based positive electrode material and a certain amount of poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) in ethanol, stirring and heating, filtering, and drying in vacuum to obtain a surface multiple modified lithium-rich manganese-based positive electrode material;
4) preparing slurry from the lithium-rich manganese-based positive electrode material, PEDOT, PSS conductive agent and adhesive in N-methyl pyrrolidone according to a certain proportion, and coating to prepare the pole piece.
Example 2: the lithium-rich manganese-based positive electrode material is prepared according to the following steps:
1) dissolving nickel sulfate, manganese sulfate and cobalt sulfate metal salt in a certain metering ratio in a certain amount of deionized water, continuously adding into a reaction kettle at a certain speed by using a peristaltic pump, and simultaneously adding Na2CO3Dropping the mixed solution with ammonia water into the reaction kettle at a certain speed, adjusting the pH environment value in the reaction kettle by controlling the dropping speed of the mixed solution and the ammonia water, carrying out coprecipitation reaction, and carrying out suction filtration, washing and drying on the obtained reaction solution after the reaction is finished to prepare a precursor of the lithium-rich manganese-based positive electrode material;
2) mixing Li2CO3Grinding and mixing the precursors according to a metered molar ratio, and calcining the mixture at a high temperature in a muffle furnace in an air atmosphere after uniformly mixing; the calcination process adopts stage temperature control, the temperature is slowly raised to 500 ℃ and kept for 5h, then the temperature is slowly raised to 900 ℃ and calcined for 12h, and the lithium-rich manganese-based anode material is obtained after the calcination is finished and is cooled at room temperature;
3) preparing a lithium-rich manganese-based positive electrode material, conductive carbon black and a binder into slurry in N-methyl pyrrolidone according to a certain proportion, and coating to prepare the pole piece.
The lithium-rich manganese-based positive electrode material pole pieces obtained in example 1 and example 2 were assembled into a snap-in battery (a metal lithium piece for a negative electrode), and charge/discharge performance and cycle performance were tested.
As can be seen from comparison of SEM images in FIG. 1, the spherical precursor material with good morphology is prepared by adopting a coprecipitation method.
Fig. 2 is a graph comparing the first charge and discharge curves at 0.1C for the materials obtained in example 1 and example 2. As can be seen from the figure, compared with the untreated material, the material subjected to surface multiple modification has higher first discharge specific capacity, the advantage of high specific capacity is kept, and the coulombic efficiency is obviously improved.
FIG. 3 is a graph comparing the cycle performance curves of the materials obtained in example 1 and example 2. As can be seen from the figure, the material treated by the surface multiple modification has better cycle performance than the untreated material.
FIG. 4 is a graph comparing the rate capability curves of the materials obtained in example 1 and example 2. As can be seen from the figure, the material subjected to the surface multiple modification treatment has higher rate performance than the untreated material.
It should be noted that the above-mentioned embodiments are only illustrative and not restrictive of the technical solutions of the present invention, and equivalents and other modifications made by those skilled in the art without departing from the spirit and scope of the technical solutions of the present invention are included in the claims of the present invention.

Claims (10)

1. A precursor of Li-rich Mn-base positive electrode material is prepared through coprecipitation, dissolving the sulfates of Ni, Co and Mn in deionized water, adding them to a reactor, adding Na solution, and adding Na solution2CO3And (3) dropping the mixed solution with ammonia water into the reaction kettle at a certain speed, adjusting the pH environment value in the reaction kettle by controlling the dropping speed of the mixed solution and the ammonia water, carrying out coprecipitation reaction, and carrying out suction filtration, washing and drying on the obtained reaction solution after the reaction is finished to prepare a solid precursor.
2. The method for modifying the lithium-rich manganese-based positive electrode material is characterized in that the precursor material according to claim 1 is uniformly mixed with a lithium salt, a sodium source and a fluorine source and then calcined to obtain the modified lithium-rich manganese-based positive electrode material.
3. The method for modifying the lithium-rich manganese-based positive electrode material is characterized in that the obtained modified positive electrode material is mixed with the conductive polymer in the dispersion liquid again according to the claim 2, and the coated modified lithium-rich manganese-based positive electrode material is obtained after heating, stirring, filtering and vacuum drying.
4. The method for modifying a lithium-rich manganese-based positive electrode material according to claim 1, wherein a certain amount of ammonium bicarbonate is added to the reaction vessel system.
5. The method for modifying a lithium-rich manganese-based positive electrode material according to claim 2, wherein the molar ratio of the precursor to the lithium salt is 1:1.4, and the lithium salt is at least one of lithium carbonate, lithium hydroxide and lithium fluoride.
6. The method for modifying a lithium-rich manganese-based positive electrode material according to claim 2, wherein the sodium source is at least one of sodium carbonate, sodium bicarbonate and sodium sulfide; the fluorine source is at least one of lithium fluoride, sodium fluoride and ammonium fluoride.
7. The method for modifying the lithium-rich manganese-based positive electrode material as claimed in claim 2, wherein the temperature is raised to 500 ℃ per minute at a rate of 3 ℃ during calcination, the temperature is maintained for 5 hours, and then the temperature is raised to 900 ℃ per minute at a rate of 4 ℃ during calcination for 12 hours to obtain the lithium-rich manganese-based positive electrode material.
8. The method for modifying a lithium-rich manganese-based positive electrode material according to claim 3, wherein the dispersion liquid is at least one of water, N-methylpyrrolidone, and ethanol; the heating temperature is 40-80 ℃; the vacuum drying temperature is 60-100 ℃.
9. The method for modifying the lithium-rich manganese-based positive electrode material according to claim 3, wherein the conductive polymer is poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT: PSS), the coating amount of the PEDOT: PSS is 1% -10%, and the surface multiple-modification modified lithium-rich manganese-based positive electrode material coated with the PEDOT: PSS is obtained.
10. The modified lithium-rich manganese-based positive electrode material as claimed in claims 1 to 9, wherein when used for a positive electrode plate of a lithium ion battery, the material is prepared by using the following steps of PEDOT: PSS is used as a conductive agent.
CN201911201192.1A 2019-11-29 2019-11-29 Method for modifying lithium-rich manganese-based positive electrode material Pending CN111056578A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112542582A (en) * 2020-12-09 2021-03-23 四川虹微技术有限公司 Multi-element modified lithium-rich manganese-based positive electrode material and preparation method thereof
CN113363484A (en) * 2021-05-20 2021-09-07 贵州梅岭电源有限公司 Method for improving coulombic efficiency and cycle stability of lithium-rich cathode material
CN114243009A (en) * 2021-12-20 2022-03-25 蜂巢能源科技股份有限公司 Positive electrode material and preparation method and application thereof
WO2024037261A1 (en) * 2023-07-13 2024-02-22 广东邦普循环科技有限公司 Preparation method for double-layer coated lithium-sodium composite lithium-rich manganese-based positive electrode material

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112542582A (en) * 2020-12-09 2021-03-23 四川虹微技术有限公司 Multi-element modified lithium-rich manganese-based positive electrode material and preparation method thereof
CN112542582B (en) * 2020-12-09 2021-09-28 四川虹微技术有限公司 Multi-element modified lithium-rich manganese-based positive electrode material and preparation method thereof
CN113363484A (en) * 2021-05-20 2021-09-07 贵州梅岭电源有限公司 Method for improving coulombic efficiency and cycle stability of lithium-rich cathode material
CN114243009A (en) * 2021-12-20 2022-03-25 蜂巢能源科技股份有限公司 Positive electrode material and preparation method and application thereof
CN114243009B (en) * 2021-12-20 2024-03-29 蜂巢能源科技股份有限公司 Positive electrode material and preparation method and application thereof
WO2024037261A1 (en) * 2023-07-13 2024-02-22 广东邦普循环科技有限公司 Preparation method for double-layer coated lithium-sodium composite lithium-rich manganese-based positive electrode material

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WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20200424