CN117038888A - Method for carrying out structural optimization on lithium-rich positive electrode material by adopting high-valence ion doping - Google Patents

Method for carrying out structural optimization on lithium-rich positive electrode material by adopting high-valence ion doping Download PDF

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CN117038888A
CN117038888A CN202310989725.7A CN202310989725A CN117038888A CN 117038888 A CN117038888 A CN 117038888A CN 202310989725 A CN202310989725 A CN 202310989725A CN 117038888 A CN117038888 A CN 117038888A
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lithium
source
positive electrode
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doped
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边筱扉
张彤
李文剑
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Dongguan University of Technology
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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
    • H01M4/36—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
    • 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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • 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

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Abstract

The invention discloses a method for optimizing the structure of a lithium-rich positive electrode material by adopting high-valence ion doping, which prepares pure-phase Li by a sol-gel method 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 The material is used for preparing the positive electrode material Li of the lithium-rich manganese-oxygen lithium ion battery by a sol-gel method 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 By Ce 4+ Doping and modifying. Then adopting an X-ray diffractometer and a scanning electron microscope to analyze the structure and morphology of the prepared material, performing constant-current charge and discharge test and cyclic voltammetry test, and analyzing Ce from the test result 4+ Doping to Li 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 The electrochemical properties of the material. Ce (Ce) 4+ The first charge specific capacity of the material before and after doping was substantially unchanged, but compared to the first discharge specific capacity of the undoped material (249.5 mAh g ‑1 )，Ce 4+ Specific charge of the doping material (257.2 mAh g ‑1 ) And the improvement is achieved. It can be seen that Ce is doped 4+ Can improve Li 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 First coulombic efficiency of the material. The discharge plateau of undoped material decays very fast but is doped with Ce 4+ After that, the rate of decay of the discharge plateau of the material is significantly slowed down.

Description

Method for carrying out structural optimization on lithium-rich positive electrode material by adopting high-valence ion doping
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a method for carrying out structural optimization on a lithium-rich positive electrode material by adopting high-valence ion doping.
Background
The lithium ion battery is widely applied to daily life of people, but the rapid development of the scientific society makes the performance of the low-energy-density lithium ion battery in the present stage not meet the use requirement of human beings, and the cathode material, electrolyte and diaphragm can meet the use requirement in the present stage in key parts for determining the performance of the lithium ion battery. However, in the positive electrode material which is the main stream at this stage, liMO 2 (m=co, ni, mn) is costly to produce and is relatively toxic, liMn 2 O 4 Is not high enough, liFePO 4 The energy density and the electron conductivity of the material are low, and the defects of the material are main factors for restricting the performance of the lithium ion battery.
Lithium-rich manganese oxide materials are expected to become hot spots in positive electrode materials by virtue of their very high specific capacity and energy density. However, this material also has some drawbacks: (1) the cycle performance is not ideal. Li during charging 2 MnO 3 Li in the component + Release with oxygen can cause the material to gradually transition to a spinel structure; (2) the rate capability is not high enough. Li (Li) 2 MnO 3 Is an important component of the lithium-rich manganese oxide material, but has lower electron conductivity, which also results in low rate capability of the lithium-rich manganese oxide material; (3) During cycling, the discharge capacity and the rate of discharge plateau decrease very rapidly.
Research on how to overcome these problems is of great importance for improving the performance of lithium ion batteries.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for optimizing the structure of a lithium-rich positive electrode material by adopting high-valence ion doping to improve the performance of a lithium ion battery.
In order to achieve the above purpose, the technical scheme adopted by the invention is that the method for optimizing the structure of the lithium-rich anode material by adopting high-valence ion doping comprises the following steps:
(1) Preparing 10-15 wt% citric acid aqueous solution by using citric acid and lithium carbonate according to a molar ratio of 1.2:1-2:1;
(2) According to Li 1.18 Ni 0.15 Co 0.15 Mn 0.52-x Ce x O 2 Is to weigh cerium source, lithium source, cobalt source, nickel source and manganese source, wherein 0<x is less than or equal to 0.03, and is prepared into a solution together with deionized water and absolute ethyl alcohol, the prepared citric acid aqueous solution is dripped into the solution, and the pH value is regulated to about 7.0 to 7.5 by ammonia water;
(3) Continuously stirring the solution obtained in the step (1) at 50-80 ℃ until gel is formed;
(4) Drying the gel obtained in the step (2) for 10-12 hours at 100-150 ℃ in a vacuum environment;
(5) Presintering the dried material for 5-7 h at 350-450 ℃, taking out and compacting, sintering the compacted material for 10-14 h at 800-1000 ℃, and quenching the sinter in a liquid nitrogen environment to finally obtain Ce 4+ Doped lithium-rich cathode material.
Preferably, in the step (2), the volume ratio of deionized water to absolute ethyl alcohol is 2:1-3:1; the solid-to-liquid ratio of the lithium source to the absolute ethyl alcohol is 1g:25 mL-1 g:30mL.
Preferably, the cerium source is cerium nitrate and the lithium source is lithium carbonate; the cobalt source, nickel source and manganese source are acetates of cobalt, nickel and manganese, respectively.
The invention has the beneficial effects that: ce (Ce) 4+ Doping modified Li 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 Materials and undoped modified Li 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 The XRD patterns of the materials remained substantially consistent, no new diffraction peaks were observed, thus indicating Ce 4+ Is not to lead to Li 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 The crystal structure of the material changes significantly. Before doping modification, the materialThe grain diameter of the particles is between 200 and 400nm, and Ce is doped 4+ After that, the particle shape of the material is not changed significantly, but the size of the material is increased, between 200 and 700nm, doped Ce 4+ Promoting the crystal growth of the material. Ce (Ce) 4 + The first charge specific capacity of the material before and after doping was substantially unchanged, but compared to the first discharge specific capacity of the undoped material (249.5 mAh g -1 )，Ce 4+ Specific charge of the doping material (257.2 mAh g -1 ) And the improvement is achieved. It can be seen that Ce is doped 4+ Can improve Li 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 First coulombic efficiency of the material. The discharge plateau of undoped material decays very fast but is doped with Ce 4+ After that, the rate of decay of the discharge plateau of the material is significantly slowed down.
Drawings
FIG. 1 is Ce 4+ Before and after doping Li 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 XRD pattern of the material;
FIG. 2 is Ce 4+ Before and after doping Li 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 SEM images of the material; FIG. 2 (a) is Li 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 SEM of the material, FIG. 2 (b) is Ce 4+ Doped Li 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 SEM images of the material;
FIG. 3 is Ce 4+ Before and after doping Li 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 A first charge-discharge curve of the material;
FIG. 4 is Ce 4+ Before and after doping Li 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 A comparison graph of the cycle performance of the material at 0.2C magnification;
FIG. 5 is pure phase Li 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 Materials and Ce 4+ Doped Li 1.18 Ni 0.15 Co 0.15 Mn 0.51 Ce 0.01 O 2 A magnification performance diagram of the material;
FIG. 6 is Ce 4+ Before and after doping Li 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 CV diagrams of materials at different scan rates.
Detailed Description
The present invention will be further described with reference to specific examples, but the scope of the present invention is not limited thereto.
Example 1
A method for optimizing the structure of a lithium-rich positive electrode material by adopting high-valence ion doping comprises the following steps:
(1) Adding citric acid and lithium carbonate into water according to a molar ratio of 2:1 to prepare a citric acid aqueous solution (the concentration of citric acid is 10 wt%);
(2) According to Li 1.18 Ni 0.15 Co 0.15 Mn 0.51 Ce 0.01 O 2 Cerium nitrate, lithium carbonate and acetate of cobalt, nickel and manganese are weighed according to the stoichiometric ratio, and are prepared into a solution together with deionized water and absolute ethyl alcohol (the volume ratio of the deionized water to the absolute ethyl alcohol is 2:1; the solid-to-liquid ratio of the lithium carbonate to the absolute ethyl alcohol is 1g:30 mL), the prepared aqueous solution of citric acid is dropwise added into the solution, and the pH value is regulated to about 7.3 by ammonia water;
(3) Continuously stirring the solution obtained in the step (1) at 50 ℃ until gel is formed;
(4) Drying the gel obtained in the step (2) for 12 hours at 120 ℃ in a vacuum environment;
(5) Presintering the dried material at 450 ℃ for 5 hours, taking out and compacting, sintering the compacted material at 900 ℃ for 12 hours, and quenching the sinter in a liquid nitrogen environment to finally obtain Ce 4+ Doped Li 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 Material (Ce) 4+ Doped lithium-rich positive electrode material).
Comparative example 1
Comparative example 1 differs from example 1 in that: according to Li in step (2) 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 Is to weigh lithium carbonate and acetate of cobalt, nickel and manganeseAnd preparing the solution with deionized water and absolute ethyl alcohol.
FIG. 1 is pure phase and Ce 4+ Doped Li 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 XRD patterns of the materials, from which both materials can be observed to have sharp diffraction peaks, indicate that the crystallinity of the materials is good. From the XRD pattern, it can be seen that no significant impurities exist in the material, and Li 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 The material has a chemical structure with LiCoO 2 Similar alpha-NaFeO 2 A layered structure. Some weak diffraction peaks can be observed between 2θ=20° and 25 °, which originate from Li 2 MnO 3 The Li atoms and Mn atoms in the composition alternately arrange in the transition metal layer to form a superlattice structure. Comparison can be seen to show Ce 4+ Doping modified Li 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 Materials and undoped modified Li 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 The XRD patterns of the materials remained substantially consistent, no new diffraction peaks were observed, thus indicating Ce 4+ Is not to lead to Li 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 The crystal structure of the material changes significantly.
FIG. 2 is Ce 4+ Before and after doping Li 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 SEM images of the material; in FIG. 2, (a) is Li 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 SEM of the material, FIG. 2 (b) is Ce 4+ Doped Li 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 SEM image of the material. SEM pictures of the two materials are observed, and the particles of the two materials are irregular polyhedrons, the surfaces of the two materials are smooth, and the edges and corners of the two materials are clear. Before doping modification, the particle size of the material particles is between 200 and 400nm, and Ce is doped 4+ After that, the particle shape of the material was not significantly changed, but the size of the material was increased to between 200 and 700nm, which may be doped Ce 4+ Promote crystal growth of the material。
Pure phase Li 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 Material and Ce 4+ Doped Li 1.18 Ni 0.15 Co 0.15 Mn 0.51 Ce 0.01 O 2 The first charge-discharge curve of the material is shown in fig. 3. Through observation and analysis, it is found that the charging voltage of 4.5V can be used as the demarcation point for Li 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 The first charge curve of a material is roughly divided into two parts, which correspond to two different reaction phases of the material during charging: (1) During the gradual rise of the charging voltage to 4.5V, nickel cobalt ions in the material are oxidized to higher valence state, wherein the oxidized nickel cobalt ions mainly come from LiMO 2 A component (C); when the voltage rises above 4.5V, another component Li of the material 2 MnO 3 Has the reactivity and releases Li + O and O 2 。Ce 4+ The first charge specific capacity of the material before and after doping was substantially unchanged, but compared to the first discharge specific capacity of the undoped material (249.5 mAh g -1 )，Ce 4+ Specific charge of the doping material (257.2 mAh g -1 ) And the improvement is achieved. It can be seen that Ce is doped 4+ Can improve Li 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 First coulombic efficiency of the material. It can also be seen from the figure that the discharge plateau of undoped material decays very rapidly, but is doped with Ce 4+ After that, the rate of decay of the discharge plateau of the material is significantly slowed down.
FIG. 4 is Ce 4+ Before and after doping Li 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 Comparison of the cycling performance of the material at 0.2C magnification. The detailed data of the current cycle performance test have been listed in tabular form as shown in table 1. The capacity loss of the undoped material after 50 times of circulation is 56.6mAh g -1 The capacity retention was 77%; and Ce (Ce) 4+ Doped Li 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 The lost capacity after 50 times of material circulation is only 27.8mAh g -1 OnlyThere is half of the undoped material and the capacity retention is increased to 89%. Experimental results show that Ce is doped 4+ Can improve Li 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 The material has circulation stability. The reason for the improved cycle performance is Ce 4+ The radius of the catalyst is larger than that of nickel cobalt manganese ions, and the catalyst can play a role of a supporting structure in the material, so that the structure of the material is Li + The structure is kept stable without collapsing in the process of de-embedding.
Table 1 constant current charge and discharge test data
FIG. 5 is pure phase Li 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 Materials and Ce 4+ Doped Li 1.18 Ni 0.15 Co 0.15 Mn 0.51 Ce 0.01 O 2 Multiplying power performance diagram of material, and can be found by observing multiplying power performance diagrams of two materials 4+ The discharge performance of the doped and modified sample under different charge-discharge multiplying power is better than that of the undoped sample. Table 2 lists Li 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 Materials and Li 1.18 Ni 0.15 Co 0.15 Mn 0.51 Ce 0.01 O 2 Discharge capacity at different charge-discharge rates. Experimental results show that Ce 4+ Doping can improve Li 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 The multiplying power performance of the material is due to the doping of Ce 4+ The ions can broaden Li in the material + Is more beneficial to Li + Is inserted into and removed from the housing.
TABLE 2 discharge capacities of undoped and doped materials at different magnifications
FIG. 6 is Ce 4+ Before and after doping Li 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 CV of the material at different scan rates, in FIG. 6, (a) and (b) are undoped material and Ce 4+ CV plots of the previous three cycles of dopant material, each scanned at a rate of 0.1mVs -1 . From a view of the first cycle voltammetric curve, two oxidation peaks can be seen in the curve of the charged portion: one is an oxidation peak at about 4.0V, which is associated with oxidation of nickel and cobalt ions in the material; the other is an oxidation peak around 4.6V, and Li 2 MnO 3 The components being activated, the process being reactive, li + Irreversibly taken off with O in the crystal lattice 2- Is oxidized to release O 2 。Li 2 MnO 3 The oxygen release process in the component is accompanied by the structural transformation of the lithium-rich manganese oxide positive electrode material from the lamellar phase to the spinel phase. Li (Li) 1.18 Ni 0.15 Co 0.15 Mn 0.52 O 2 Three reduction peaks exist in the first discharge process of the material, wherein the reduction peaks at about 3.65V and about 4.4V are respectively matched with Ni 4+ Reduction to Ni 2+ Co and method for producing the same 4+ Reduction to Co 3+ Is related to the process of (a), and the reduction peak of about 3.2V is related to Mn 4+ The reduction to a lower valence state is relevant. From the CV diagram, two differences in cyclic voltammograms of the two materials can be observed: the oxidation potential of lattice oxygen of the doped and modified material is increased from 4.61V to 4.66V, which shows that the doping of Ce to Li 2 MnO 3 Middle O 2- Has an inhibitory effect on oxidation of (a). Second, ni in the second and third cycles of the doping material 2+ And Co 3+ Is significantly shifted compared with the first cycle, the oxidation peak potential is reduced, which indicates Ce 4+ The polarization degree of the doped material is reduced, and the structural stability is better.
In FIG. 6, (c) and (d) are pure phase materials and Ce 4+ Doping material at 1mVs -1 CV diagram at scan rate. It can be seen from the figure that the peak pattern of the undoped material is completely distorted at this time, indicating that the chemical reaction of the material is incomplete; and at Ce 4+ Relatively obvious oxidation peaks and reduction peaks can be observed in CV diagram of the doped material, which shows thatThe reaction in the material is more complete. This phenomenon occurs because of the doped Ce 4+ Can play the role of a supporting structure in the material, and can store Li + The transmission channel of the (C) is opened, which is more beneficial to the electrochemical reaction.
Example 2
A method for optimizing the structure of a lithium-rich positive electrode material by adopting high-valence ion doping comprises the following steps:
(1) Adding citric acid and lithium carbonate into water according to a molar ratio of 1.2:1 to prepare a citric acid aqueous solution (the concentration of citric acid is 15 wt%); (2) According to Li 1.18 Ni 0.15 Co 0.15 Mn 0.49 Ce 0.03 O 2 Weighing cerium nitrate, lithium carbonate and acetate of cobalt, nickel and manganese, preparing a solution with deionized water and absolute ethyl alcohol (the volume ratio of the deionized water to the absolute ethyl alcohol is 3:1; the solid-to-liquid ratio of the lithium carbonate to the absolute ethyl alcohol is 1g:25 mL), dripping the prepared aqueous solution of citric acid into the solution, and regulating the pH value to about 7.0 by ammonia water;
(3) Continuously stirring the solution obtained in the step (1) at 60 ℃ until gel is formed;
(4) Drying the gel obtained in the step (2) for 12 hours at 100 ℃ in a vacuum environment;
(5) Presintering the dried material at 350 ℃ for 7 hours, taking out and compacting, sintering the compacted material at 800 ℃ for 4 hours, and quenching the sinter in a liquid nitrogen environment to finally obtain Ce 4+ Doped lithium-rich cathode material.
Example 3
A method for optimizing the structure of a lithium-rich positive electrode material by adopting high-valence ion doping comprises the following steps:
(1) Adding citric acid and lithium carbonate into water according to a molar ratio of 1.5:1 to prepare a citric acid aqueous solution (the concentration of the citric acid is 12 wt%);
(2) According to Li 1.18 Ni 0.15 Co 0.15 Mn 0.50 Ce 0.02 O 2 Cerium nitrate, lithium carbonate and acetates of cobalt, nickel and manganese are weighed in stoichiometric ratio, and are prepared into solution together with deionized water and absolute ethyl alcohol (deionized water and absolute ethyl alcohol)Is 2.5:1 by volume; the solid-to-liquid ratio of lithium carbonate to absolute ethyl alcohol is 1g:27 mL), the prepared citric acid aqueous solution is dripped into the solution, and the pH value is regulated to about 7.5 by ammonia water;
(3) Continuously stirring the solution obtained in the step (1) at 80 ℃ until gel is formed;
(4) Drying the gel obtained in the step (2) at 150 ℃ for 10 hours in a vacuum environment;
(5) Presintering the dried material at 400 ℃ for 6 hours, taking out and compacting, sintering the compacted material at 1000 ℃ for 10 hours, and quenching the sinter in a liquid nitrogen environment to finally obtain Ce 4+ Doped lithium-rich cathode material.

Claims (4)

1. The method for carrying out structural optimization on the lithium-rich positive electrode material by adopting high-valence ion doping is characterized by comprising the following steps of:
(1) Preparing 10-15 wt% citric acid aqueous solution by using citric acid and lithium carbonate according to a molar ratio of 1.2:1-2:1;
(2) According to Li 1.18 Ni 0.15 Co 0.15 Mn 0.52-x Ce x O 2 Is to weigh cerium source, lithium source, cobalt source, nickel source and manganese source, wherein 0<x is less than or equal to 0.03, and is prepared into a solution together with deionized water and absolute ethyl alcohol, the prepared citric acid aqueous solution is dripped into the solution, and the pH value is regulated to about 7.0 to 7.5 by ammonia water;
(3) Continuously stirring the solution obtained in the step (1) at 50-80 ℃ until gel is formed;
(4) Drying the gel obtained in the step (2) for 10-12 hours at 100-150 ℃ in a vacuum environment;
(5) Presintering the dried material for 5-7 h at 350-450 ℃, taking out and compacting, sintering the compacted material for 10-14 h at 800-1000 ℃, and quenching the sinter in a liquid nitrogen environment to finally obtain Ce 4+ Doped lithium-rich cathode material.
2. The method for structural optimization of lithium-rich positive electrode materials by high valence ion doping according to claim 1, wherein the method comprises the following steps: in the step (2), the volume ratio of deionized water to absolute ethyl alcohol is 2:1-3:1.
3. The method for structural optimization of lithium-rich positive electrode materials by high valence ion doping according to claim 2, wherein the method comprises the following steps: in the step (2), the solid-to-liquid ratio of the lithium source to the absolute ethyl alcohol is 1g:25 mL-1 g:30mL.
4. The method for structural optimization of lithium-rich positive electrode materials by high valence ion doping according to claim 1, wherein the method comprises the following steps: the cerium source is cerium nitrate, and the lithium source is lithium carbonate; the cobalt source, nickel source and manganese source are acetates of cobalt, nickel and manganese, respectively.
CN202310989725.7A 2023-08-07 2023-08-07 Method for carrying out structural optimization on lithium-rich positive electrode material by adopting high-valence ion doping Pending CN117038888A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117691095A (en) * 2024-02-01 2024-03-12 吉林大学 Lithium-rich all-solid-state battery positive electrode material, preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117691095A (en) * 2024-02-01 2024-03-12 吉林大学 Lithium-rich all-solid-state battery positive electrode material, preparation method and application thereof
CN117691095B (en) * 2024-02-01 2024-04-23 吉林大学 Lithium-rich all-solid-state battery positive electrode material, preparation method and application thereof

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