CN109560265B - Coating method for effectively inhibiting oxygen loss of lithium-rich manganese-based positive electrode material - Google Patents
Coating method for effectively inhibiting oxygen loss of lithium-rich manganese-based positive electrode material Download PDFInfo
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Abstract
A coating method for effectively inhibiting oxygen loss of a lithium-rich manganese-based positive electrode material belongs to the field of positive electrode materials of lithium ion batteries. The method comprises the following steps: 1) uniformly dispersing the prepared lithium-rich manganese-based positive electrode material in deionized water or other organic solvents by ultrasonic; 2) respectively dissolving molybdate and manganese salt into an organic solvent or deionized water to prepare solutions; 3) simultaneously dropwise adding a molybdate solution and a manganite solution into the dispersion liquid of the lithium-rich material under the condition of water bath, and adjusting the pH of the solution to enable the molybdate and the manganite to generate manganese molybdate which is deposited on the surface of the lithium-rich material in situ; 4) calcining the filtered, washed and dried coating material at the temperature of 450-600 ℃ for 4-6h, cooling to room temperature to finally obtain MnMoO4And (3) a coated lithium-rich manganese-based positive electrode material. The method comprises the step of depositing MnMoO4The lithium-rich manganese-based positive electrode material is coated on the surface of the lithium-rich manganese-based positive electrode material in situ, the process is simple, the cost is low, the oxygen loss of the material in the first charge-discharge process can be effectively inhibited, the coulombic efficiency and the cycle performance of the material are obviously improved, and the lithium-rich manganese-based positive electrode material has a wide application prospect.
Description
Technical Field
The invention belongs to the field of lithium ion battery anode materials, and particularly relates to a coating method for effectively inhibiting oxygen loss of a lithium-rich manganese-based anode material and application of the coating method in a lithium ion battery.
Background
With the gradual depletion of fossil energy and the increasingly serious environmental problems, the development and use of clean energy is a hot topic of today's society. Although clean renewable energy sources such as solar energy, wind energy and tidal energy can hopefully replace traditional energy sources, the clean renewable energy sources have the characteristics of intermittency and uncertainty and are difficult to directly utilize, so that the clean energy sources need to be stored and converted into secondary energy sources such as electric energy, chemical energy and the like, and secondary batteries are produced at the same time. Lithium ion batteries are currently the most widely used secondary batteries due to their high energy density and good cycling stability. With the continuous development and progress of society, the energy demand is gradually increased, and people have higher requirements on the performance of lithium ion batteries. Since the lithium-rich layered oxide is developed to the present in 2006, the lithium-rich layered oxide becomes the most potential next-generation lithium ion battery cathode material due to the ultrahigh specific capacity of more than 250 mAh/g.
In the novel xLi2MnO3·(1-x)LiMO2In the process of charging and discharging the composite material, the first irreversible capacity loss is large, the first efficiency is low, and the charging curve of the composite material in the first cycle is obviously different from the charging curve of the composite material in the subsequent cycle. During the first charge of a material, there are two distinct plateaus in the charge curve: 3.8-4.4V (vs. Li)+Li), this platform is present by LiMO in the material2Produced by oxidation of the transition metals Ni and Co in the composition, with Li+Is derived from Ni2+And Co3+Is oxidized into Ni4+And Co4+The reaction mechanism of this process can be explained by the mechanism of lithium intercalation and deintercalation of the conventional layered material, i.e. LiMO2→Li++MO2+ e; when the voltage exceeds 4.5V (vs. Li)+Li), a second plateau appears, and for the reason of this plateau, researchers mostly consider it to be associated with another component Li in the composite material2MnO3And (4) correlating. At this stage, the widely accepted mechanism for the platform of the lithium-rich manganese-based material at 4.5V is as follows: as charging proceeds, Li+Continue to use from Li2MnO3(C2/m space group) with O2The free oxygen liberated is lost by interaction with the electrolyte and cannot be completely inserted back into the solid solution phase, oxygen vacancies are lost, leading to the liberated Li during the discharge phase+Can not be completely inserted back into the solid solution phase, and the first charge-discharge capacity loss is finally expressed as Li+With Li2O is in the form of Li2MnO3Phase separation, the so-called "oxygen loss" mechanism.
The ultra-high specific capacity of the lithium-rich manganese-based positive electrode material is attributed to the redox reaction of the transition metal and the anion (O)2-) Charge compensation mechanism of (1). The redox process of the transition metal has good reversibility, and the redox process of the transition metal is carried out in a high-voltage charging process of about 4.5VCrude anion (O)2-) Oxidation process of (2), finally forming O2The release of molecules from the bulk of the material causes severe oxygen loss and irreversible capacity loss. This causes migration and rearrangement of transition metal ions to the inner layer, causing phase transition during cycling, resulting in voltage and capacity decay, and release of O2Side reactions with the electrolyte may occur to form an unstable SEI film, which deteriorates the kinetic parameters of the electrode material, and these problems seriously hinder the commercialization process of the lithium-rich material. Therefore, the method is particularly key to improve the specific capacity and structural stability of the material and inhibit oxygen loss of the material in the first-turn activation process. Therefore, people adopt various means to carry out modification optimization treatment on the lithium-rich material, so as to inhibit oxygen loss of the lithium-rich material and improve the electrochemical performance of the material.
Disclosure of Invention
The invention aims to solve the problem of oxygen loss in the first activation process of a lithium-rich manganese-based positive electrode material, and provides a method for coating MnMoO on the surface4Means for effectively inhibiting oxygen loss from lithium-rich materials. The method comprises the steps of depositing molybdate precipitates on the surface of a lithium-rich material (LLO) in situ, and then calcining a precursor material of molybdenum to generate MnMoO with good crystal form4Coating to obtain LLO @ MnMoO4A composite material. The invention utilizes the advantages of high efficiency and rapidness of wet chemical deposition reaction and combines MnMoO with rich oxygen cavities4A method for effectively inhibiting oxygen loss of a lithium-rich manganese-based positive electrode material is developed.
The invention is realized by the following technical scheme:
a coating method for effectively inhibiting oxygen loss of a lithium-rich manganese-based positive electrode material is characterized by comprising the following steps of:
(1) ultrasonically dispersing the prepared lithium-rich manganese-based positive electrode material in deionized water or other organic solution;
(2) respectively dissolving molybdate and manganese salt into an organic solvent or deionized water to prepare solutions;
(3) under the condition of water bath, solutions of molybdate and manganese salt are simultaneously dripped into the dispersion liquid of the lithium-rich material, and the pH of the solution is controlled to be 8-11 by adding ammonia water, so that molybdate radicals and manganese ions are subjected to double decomposition reaction and are in-situ deposited on the surface of the lithium-rich material;
(4) calcining the filtered, washed and dried precursor coating material at high temperature, and cooling to room temperature to finally obtain MnMoO4And (3) a coated lithium-rich manganese-based positive electrode material.
Further, in the step (1), the lithium-rich manganese-based positive electrode material has a chemical formula of xLi2MnO3·(1-x)LiMO2Wherein M is at least two of Ni, Co and Mn, and x is more than or equal to 0.2 and less than or equal to 0.8; preferably Li1.2[Mn0.54Ni0.13Co0.13]O2。
Further, in the step (2), the molybdate is ammonium molybdate, phosphomolybdic acid, sodium molybdate and the like, and the manganese salt is manganese sulfate, manganese chloride, manganese nitrate and the like.
Further, the solvent in the step (2) is deionized water, ethanol, ethylene glycol and other solvents, and the concentration of the molybdenum salt solution is 1-5 g/L.
Further, the water bath reaction temperature of the solution in the step (3) is 60-80 ℃.
Further, the MnMoO in the step (3)4The amount of coating (b) is 1 wt% to 10 wt%, preferably 2 wt% to 5 wt%, relative to the lithium-rich positive electrode material.
Further, the calcining temperature in the step (4) is 450-600 ℃, and the calcining time is 4-6 h.
MnMoO prepared by the method4The coated lithium-rich manganese-based positive electrode material is applied to a lithium ion battery as an electrode material.
The mechanism of the invention is as follows:
o charge compensated according to the reversible redox mechanism of oxygen2-O is formed only on the surface layer2So long as the surface is coated with a layer of material with rich oxygen cavities, O will be generated2Or O(2-n)Storage on the surface of the material prevents its release, thus inhibiting the decomposition of the electrolyte, promoting the reversible reduction of the anions, increasing the specific capacity of the material and reducing the irreversibility of the materialLoss of reverse capacity. And lower valence MnMoO4Has both excellent electron conductor properties and excellent storage Li+And has rich oxygen holes, and is expected to store O generated in the first charging process of the material2Or O(2-n)And reversibly releasing oxygen in the discharging process, and enhancing the charge compensation capability of anions, thereby improving the specific capacity, coulombic efficiency and structural stability of the lithium-rich material, and being used as a novel material for effectively inhibiting oxygen loss of the lithium-rich manganese-based cathode material.
The innovation of the invention is that:
manganese molybdate is deposited on the surface of a lithium-rich material in situ by a simple and rapid precipitation method to form a uniform precursor coating layer, and then the precursor coating layer is placed in an atmosphere furnace for annealing and calcination to prepare MnMoO4Coated lithium-rich manganese-based positive electrode material (LLO @ MnMoO)4)。MnMoO4The rich oxygen holes can effectively store oxygen released by the lithium-rich material in the first activation process and promote the reversible reduction of the lithium-rich material, so that the coulombic efficiency and the integrity of an oxygen array of the lithium-rich material are improved, and the oxygen loss behavior of the lithium-rich manganese-based positive electrode material in the charging and discharging processes can be effectively inhibited.
Drawings
Fig. 1 is an X-ray diffraction (XRD) pattern of the lithium-rich manganese-based positive electrode materials prepared in example 1, example 2, and comparative example 1.
Fig. 2 is a Scanning Electron Microscope (SEM) picture of the original lithium-rich manganese-based positive electrode material prepared in comparative example 1.
FIG. 3 is MnMoO prepared in example 14Scanning Electron Microscope (SEM) pictures of the coated lithium-rich manganese-based positive electrode material.
FIG. 4 is MnMoO prepared in example 24Scanning Electron Microscope (SEM) pictures of the coated lithium-rich manganese-based positive electrode material.
Fig. 5 is a graph of the first charge and discharge performance of the lithium-rich manganese-based positive electrode materials prepared in example 1, example 2, and comparative example 1.
Fig. 6 is a graph showing the cycle performance test of the lithium-rich manganese-based positive electrode materials prepared in example 1, example 2, and comparative example 1.
Detailed description of the preferred embodiment
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1: a coating method for effectively inhibiting oxygen loss of a lithium-rich manganese-based positive electrode material comprises the following steps:
(1) 1g of the prepared lithium-rich manganese-based positive electrode material (Li) is taken1.2[Mn0.54Ni0.13Co0.13]O2) Ultrasonically dispersing in 30mL of deionized water;
(2) respectively dissolving 0.0273g of ammonium molybdate and 0.0236g of manganese sulfate monohydrate into 10mL of deionized water to prepare solutions;
(3) simultaneously dropwise adding an ammonium molybdate solution and a manganese sulfate solution into a dispersion liquid of the lithium-rich material under the condition of 70 ℃ water bath, adding ammonia water to adjust the pH value of the solution to 9, and carrying out double decomposition reaction on a molybdate radical and manganese ions to deposit on the surface of the lithium-rich material in situ;
(4) calcining the filtered, washed and dried precursor coating material for 5h at 450 ℃ in an inert atmosphere, cooling to room temperature, and finally obtaining MnMoO4Coated lithium-rich manganese-based positive electrode material, in which MnMoO4The coating amount of (3%).
Example 2: a coating method for effectively inhibiting oxygen loss of a lithium-rich manganese-based positive electrode material comprises the following steps:
(1) 1g of the prepared lithium-rich manganese-based positive electrode material (Li) is taken1.2[Mn0.54Ni0.13Co0.13]O2) Ultrasonically dispersing in 30mL of deionized water;
(2) respectively dissolving 0.0182g of ammonium molybdate and 0.0157g of manganese sulfate monohydrate into 10mL of deionized water to prepare solutions;
(3) simultaneously dropwise adding an ammonium molybdate solution and a manganese sulfate solution into a dispersion liquid of the lithium-rich material under the condition of 60 ℃ water bath, adding ammonia water to adjust the pH value of the solution to 9, and carrying out double decomposition reaction on a molybdate radical and manganese ions to deposit on the surface of the lithium-rich material in situ;
(4) calcining the filtered, washed and dried precursor coating material for 5h at 450 ℃ in an inert atmosphere, cooling to room temperature, and finally obtaining MnMoO4Coated lithium-rich manganese-based positive electrode material, in which MnMoO4The coating amount of (2%).
Example 3: a coating method for effectively inhibiting oxygen loss of a lithium-rich manganese-based positive electrode material comprises the following steps:
(1) 1g of the prepared lithium-rich manganese-based positive electrode material (Li) is taken1.2[Mn0.54Ni0.13Co0.13]O2) Ultrasonically dispersing in 30mL of deionized water;
(2) 0.0456g of ammonium molybdate and 0.0393g of manganese sulfate monohydrate are respectively dissolved in 10mL of deionized water to prepare solutions;
(3) simultaneously dropwise adding an ammonium molybdate solution and a manganese sulfate solution into a dispersion liquid of the lithium-rich material under the condition of 80 ℃ water bath, adding ammonia water to adjust the pH value of the solution to 10, and carrying out double decomposition reaction on a molybdate radical and manganese ions to deposit on the surface of the lithium-rich material in situ;
(4) calcining the filtered, washed and dried precursor coating material for 5 hours at 500 ℃ in an inert atmosphere, cooling to room temperature, and finally obtaining MnMoO4Coated lithium-rich manganese-based positive electrode material, in which MnMoO4The coating amount of (2) was 5%.
Comparative example 1: lithium-rich manganese-based positive electrode material (Li)1.2[Mn0.54Ni0.13Co0.13]O2) The preparation method comprises the following steps:
(1) adding 2mol/L of nickel, cobalt and manganese sulfate (molar ratio is 0.13: 0.13: 0.54) solution and 4mol/L of potassium hydroxide solution (containing 25% of ammonia water solution) into a reactor at a uniform speed, controlling the coprecipitation reaction temperature to be 60 ℃, and carrying out the whole reaction under N2The reaction is carried out under an atmosphere. After the reaction is finished, immediately carrying out vacuum filtration, washing and drying to obtain a transition metal hydroxide precursor;
(2) and (2) fully and uniformly mixing the precursor of the transition metal hydroxide with a lithium source in a molar ratio, wherein the ratio of transition metal ions to lithium is 1: 1.5, then placing the mixture in an alumina crucible in a muffle furnace, calcining for 5 hours at 450 ℃, then heating to 900 ℃, calcining for 18 hours, and cooling to room temperature to obtain the lithium-rich manganese-based cathode material.
Test example
Assembling a half cell: the MnMoO-processed products prepared in example 1 and example 2 were mixed4The coated lithium-rich manganese-based positive electrode material and the lithium-rich manganese-based positive electrode material of the comparative example 1 are respectively mixed with Super P and PVDF according to the mass ratio of 75: the slurry was prepared at 15: 10 and coated, and then cut into 12mm diameter pole pieces, lithium metal was used as the negative electrode, and the electrolyte and separator were assembled into half cells in an argon glove box using Celgard2500 separator and LB-111 high voltage resistant electrolyte from Doudo chemical technology Co., Ltd, Suzhou.
And (3) charge and discharge test: the voltage range of charging and discharging of the button cell is 2.0-4.8V, before the cycle test, a smaller current density of 12.5mA/g is adopted for carrying out two times of activation, and then the charge and discharge cycle test is carried out under the current density of 125mA/g (0.5C) in the same voltage range. All electrochemical performance tests were performed at room temperature.
FIG. 1 is XRD patterns of example 1, example 2 and comparative example 1, and by comparison, it can be seen that three substances are layered α -NaFeO in which all three substances belong to the R-3m space group2And (5) structure. While the diffraction peak around 21 ℃ is Li belonging to the C2/m space group2MnO3And the phase shows that two phases with different components exist in the synthesized lithium-rich manganese-based cathode material at the same time. The diffraction peak is narrow and sharp, which shows that the crystal form of the material is good, and in addition, the diffraction peaks of (006)/(102) and (018)/(110) are obviously split, which shows that the material has a good layered structure. The XRD diffraction patterns of examples 1 and 2 have clear main diffraction peaks and higher intensity, I(003)/I(104)Significantly higher than comparative example 1, demonstrating the final synthesized MnMoO4The coated lithium-rich manganese-based positive electrode material has low cation mixing degree and excellent electrochemical performance.
By comparing fig. 2, 3 and 4, which respectively represent SEM images of lithium-rich manganese-based positive electrode materials of different morphologies prepared in comparative example 1, example 1 and example 2, it can be found that the positive electrode material is co-crystallized in liquid phaseThe lithium-rich material prepared by the precipitation method has an irregular polyhedral structure, clear edges and corners of particles, smooth surface and good crystallinity, and has the particle size distribution of between 150 and 300nm without obvious agglomeration. And through MnMoO4The surface of the coated material gradually becomes rough and a trace amount of nanoparticles (as shown in fig. 3) are present, indicating that MnMoO4Has been successfully coated on the surface of the lithium-rich material.
FIG. 5 is a graph of the first cycle charge and discharge performance of half cells assembled from the lithium rich materials prepared in examples 1 and 2 and comparative example 1, and it can be seen that MnMoO passes through4The specific discharge capacity and the coulombic efficiency of the coated lithium-rich material are both obviously improved, wherein the specific discharge capacity of the material in the embodiment 1 can reach 284.4mAh/g, and the coulombic efficiency is 86.4%; while the original lithium-rich material prepared in comparative example 1 had a specific discharge capacity and coulombic efficiency of only 275.9mAh/g and 79.5%. Fig. 6 is a graph of cycle performance test of half-cells assembled by lithium-rich materials prepared in example 1, example 2 and comparative example 1, wherein the high specific capacity of 212.5mAh/g can be maintained after 100 cycles of the cycle in example 1, and the capacity of the original lithium-rich material prepared in comparative example 1 is only 187mAh/g after 100 cycles of the cycle. Thus, the surface coating layer MnMoO can be seen4Can effectively inhibit the oxygen loss of the lithium-rich manganese-based positive electrode material, and is beneficial to improving the coulombic efficiency and the cycling stability of the lithium-rich manganese-based positive electrode material.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (7)
1. A coating method for effectively inhibiting oxygen loss of a lithium-rich manganese-based positive electrode material is characterized by comprising the following steps of:
(1) ultrasonically dispersing the prepared lithium-rich manganese-based positive electrode material in deionized water or other organic solvents;
(2) respectively dissolving molybdate and manganese salt into an organic solvent or deionized water to prepare solutions;
(3) simultaneously dropwise adding a molybdate solution and a manganite solution into a dispersion liquid of the lithium-rich material under the condition of water bath, and controlling the pH of the solution to be 8-11 so that a molybdate radical and manganese ions are subjected to a double decomposition reaction and are deposited on the surface of the lithium-rich material in situ;
(4) calcining the filtered, washed and dried precursor coating material, and cooling to room temperature to finally obtain MnMoO4A coated lithium-rich manganese-based positive electrode material;
the concentration of the molybdate and manganese salt solution in the step (2) is 1-5 g/L;
the water bath reaction temperature of the solution in the step (3) is 60-80 ℃.
2. The coating method for effectively inhibiting oxygen loss of the lithium-rich manganese-based positive electrode material according to claim 1, wherein in the step (1), the lithium-rich manganese-based positive electrode material has a chemical formula of xLi2MnO3·(1-x)LiMO2Wherein M is at least two of Ni, Co and Mn, and x is more than or equal to 0.2 and less than or equal to 0.8.
3. The coating method for effectively inhibiting oxygen loss of lithium-rich manganese-based positive electrode material according to claim 1 or 2, wherein the lithium-rich manganese-based positive electrode material has a chemical formula of Li1.2[Mn0.54Ni0.13Co0.13]O2。
4. The coating method for effectively inhibiting oxygen loss of the lithium-rich manganese-based positive electrode material according to claim 1, wherein the molybdate in the step (2) is ammonium molybdate, phosphomolybdic acid or sodium molybdate, and the manganese salt is manganese sulfate, manganese chloride or manganese nitrate.
5. The coating method for effectively inhibiting oxygen loss of the lithium-rich manganese-based positive electrode material according to claim 1, wherein the solvent in the step (2) is deionized water, ethanol or glycol solvent.
6. The coating method for effectively inhibiting oxygen loss of lithium-rich manganese-based positive electrode material according to claim 1, wherein said MnMoO in step (3)4The coating amount of (a) is 1 wt% to 10 wt% with respect to the lithium-rich positive electrode material.
7. The coating method for effectively inhibiting oxygen loss of the lithium-rich manganese-based positive electrode material according to claim 1, wherein the calcination temperature in the step (4) is 450-600 ℃; the calcination time is 4-6 h.
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| CN111092200A (en) * | 2019-11-13 | 2020-05-01 | 中南大学 | Li3Cr(MoO4)3Coating modified high-nickel ternary cathode material and preparation method thereof |
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| CN114792604A (en) * | 2022-03-25 | 2022-07-26 | 中国船舶重工集团公司第七一八研究所 | Manganese molybdate porous nanosheet electrode material and preparation method and application thereof |
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| CN115084485B (en) * | 2022-07-29 | 2023-08-18 | 大气(广东)科技发展有限公司 | Carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material and preparation method and application thereof |
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| CN107706400A (en) * | 2017-11-13 | 2018-02-16 | 合肥国轩高科动力能源有限公司 | A kind of nano aluminium oxide cladding and surface Lacking oxygen are modified rich lithium material and preparation method thereof |
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| CN107706400A (en) * | 2017-11-13 | 2018-02-16 | 合肥国轩高科动力能源有限公司 | A kind of nano aluminium oxide cladding and surface Lacking oxygen are modified rich lithium material and preparation method thereof |
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