CN111785959B - Spinel type lithium ion battery positive electrode active material and preparation method thereof - Google Patents

Spinel type lithium ion battery positive electrode active material and preparation method thereof Download PDF

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CN111785959B
CN111785959B CN202010742446.7A CN202010742446A CN111785959B CN 111785959 B CN111785959 B CN 111785959B CN 202010742446 A CN202010742446 A CN 202010742446A CN 111785959 B CN111785959 B CN 111785959B
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lithium ion
ion battery
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CN111785959A (en
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孙巍巍
李宇杰
郑春满
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National University of Defense 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
    • H01M4/50—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
    • 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
    • H01M4/52—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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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

The invention discloses a spinel type lithium ion battery anode active material and a preparation method thereof0.5Mn1.5O4A nanosheet, the LiNi0.5Mn1.5O4The dominant exposed crystal face of the nanosheet is a {111} crystal face; the preparation method comprises the steps of firstly selecting hexamethylenetetramine as a precipitator and mixed liquid of diethylene glycol and deionized water as a solvent, then adding manganese acetate and nickel acetate into the mixed solvent for dissolving, then carrying out solvothermal reaction, finally enabling lithium acetate to be uniformly distributed on carbonate precipitates through absolute ethyl alcohol, and sintering after evaporating the absolute ethyl alcohol to obtain the spinel type lithium ion battery anode active material. The positive active material provided by the invention can enable the lithium ion battery to have high energy density, excellent rate performance, excellent long cycle performance and rapid charge/discharge performance; the preparation method provided by the invention has the advantages of simple process and low cost, and the prepared cathode active material is used for the lithium ion battery, so that the lithium ion battery has excellent performance.

Description

Spinel type lithium ion battery positive electrode active material and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion battery preparation, in particular to a spinel type lithium ion battery anode active material and a preparation method thereof.
Background
With the continuous and rapid development in the fields of portable electronic equipment, electric automobiles and the like, the human society puts more stringent requirements on the lithium ion battery system which is widely applied at present. Therefore, the research and development of high-performance lithium ion batteries with excellent rapid charge/discharge performance, excellent long-period cycle performance under larger current and other requirements have very important significance for promoting social development.
For current lithium ion battery positive electrode active material research, LiNi0.5Mn1.5O4The lithium ion battery positive electrode active material is very popular with researchers due to higher working voltage and theoretical specific capacity, and is the most promising candidate for the next generation of commercial lithium ion battery positive electrode active material.
However, the current spinel phase positive electrode active material LiNi0.5Mn1.5O4Cycling performance, particularly at higher current densities, is poor.
Disclosure of Invention
The invention provides a spinel type lithium ion battery anode active material and a preparation method thereof, which are used for overcoming LiNi in the prior art0.5Mn1.5O4Poor cycle performance under higher current density and the like.
In order to achieve the purpose, the invention provides a spinel type lithium ion battery anode active material which is in a micro-nano hierarchical porous structure and is formed by a plurality of orthogonal LiNi0.5Mn1.5O4A plurality of said LiNi0.5Mn1.5O4The dominant exposed crystal face of the nano sheet is a {111} crystal face.
In order to achieve the above object, the present invention also provides a preparation method of a spinel type lithium ion battery cathode active material, the preparation method comprising:
s1: dissolving hexamethylenetetramine in a mixed solvent; the mixed solvent consists of diethylene glycol and deionized water;
s2: sequentially adding manganese acetate and nickel acetate into the mixed solvent, stirring until the manganese acetate and the nickel acetate are completely dissolved, pouring the obtained mixed solution into a hydrothermal kettle for solvent thermal reaction to obtain a precursor;
s3: adding lithium acetate and the precursor into absolute ethyl alcohol, stirring and evaporating to dryness, and sintering to obtain the spinel type lithium ion battery anode active material LiNi0.5Mn1.5O4。
Compared with the prior art, the invention has the beneficial effects that:
1. the spinel type lithium ion battery anode active material provided by the invention is of a micro-nano hierarchical porous structure, and the micro-nano hierarchical porous structure is more favorable for electrolyte infiltration and lithium ion rapid transmission, so that a higher active substance utilization rate is ensured in a discharging process, and the lithium ion battery is ensured to have high energy density and excellent rate capability.
2. LiNi which is a spinel phase positive electrode active material at present0.5Mn1.5O4The cycle performance, especially the cycle performance at higher current density, is poor, mainly due to the dissolution of Mn in the material and Mn3+The resulting Jahn-Teller distortion effect causes structural degradation. Aiming at the defects of the prior art, the spinel type lithium ion battery anode active material provided by the invention is prepared from a plurality of orthogonal LiNi0.5Mn1.5O4A plurality of LiNi0.5Mn1.5O4The dominant exposed crystal face of the nano sheet is a {111} crystal face and a spinel phase LiNi0.5Mn1.5O4The {111} crystal face of the positive active material is more stable relative to other crystal faces, and Mn is most difficult to dissolve out on the {111} crystal face, so that the dissolution of Mn can be limited to the greatest extent fundamentally by using the positive active material provided by the invention, and the excellent long-cycle performance and the rapid charge/discharge performance of the lithium ion battery are ensured.
3. The preparation method of the spinel type lithium ion battery anode active material provided by the invention comprises the following steps of firstly, selecting hexamethylenetetramine as a precipitator and mixed liquid of diethylene glycol and deionized water as a solvent; then adding manganese acetate and nickel acetate into a mixed solvent for dissolving, and then carrying out a solvothermal reaction, wherein in the solvothermal reaction, the mixed solvent of diethylene glycol and deionized water has a high steric hindrance effect, so that primary crystal nuclei can be effectively prevented from approaching each other, and hexamethylenetetramine as a precipitator is heated and slowly decomposed to generate CO2Mn in manganese acetate and nickel acetate2+、Ni2+With CO2Carbonate precipitate (namely precursor) is generated by the reaction, and the hexamethylene tetramine can be slowly decomposed to generate CO2So that the precipitation reaction of the manganese acetate and the nickel acetate can be slowly carried out, and the obtained carbonate precipitate has uniform size and shape; in addition, diethylene glycol molecules can be preferentially adsorbed on a certain crystal face of the carbonate precipitate, and gibbs of the crystal face are reducedThe free energy of Si enables crystal grains to grow along a specific crystal face, thereby being beneficial to the formation of an orthogonal nanosheet structure; and finally, uniformly distributing lithium acetate on the carbonate precipitate through absolute ethyl alcohol, evaporating the absolute ethyl alcohol, and then sintering to obtain the spinel type lithium ion battery anode active material with good crystallinity and no other impurity phases. The preparation method provided by the invention has the advantages of simple process and low cost, and the prepared anode active material is of a micro-nano hierarchical porous structure and is prepared from a plurality of orthogonal LiNi0.5Mn1.5O4A plurality of said LiNi0.5Mn1.5O4The dominant exposed crystal face of the nanosheet is a {111} crystal face, and when the positive active material is used in a lithium ion battery, the lithium ion battery has high energy density, excellent rate capability, excellent long-cycle performance and rapid charge/discharge performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 shows LiNi, a positive electrode active material of a spinel-type lithium ion battery prepared in example 10.5Mn1.5O4XRD spectrum of (1);
FIG. 2a is an SEM picture of the precursor prepared in example 1 at 10 μm;
FIG. 2b is an SEM picture of the precursor prepared in example 1 at 4 μm;
FIG. 2c shows LiNi prepared in example 10.5Mn1.5O4SEM pictures at 4 μm;
FIG. 2d is a LiNi prepared in example 10.5Mn1.5O4SEM pictures at 1 μm;
FIG. 3 is a LiNi prepared in example 10.5Mn1.5O4A TEM picture of (4);
FIG. 4 is a LiNi prepared in example 10.5Mn1.5O4The element distribution picture of (1);
FIG. 5 is a LiNi prepared in example 10.5Mn1.5O4A cycle performance curve diagram of the lithium ion battery as the anode;
FIG. 6 is a LiNi prepared in example 10.5Mn1.5O4And the performance diagram is used as the rate capability diagram of the lithium ion battery of the positive electrode.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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.
In addition, the technical solutions in the embodiments of the present invention may be combined with each other, but it must be based on the realization of those skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination of technical solutions should not be considered to exist, and is not within the protection scope of the present invention.
The drugs/reagents used are all commercially available without specific mention.
The invention provides a spinel type lithium ion battery anode active material which is in a micro-nano hierarchical porous structure and is composed of a plurality of orthogonal LiNi0.5Mn1.5O4A plurality of said LiNi0.5Mn1.5O4The dominant exposed crystal face of the nano sheet is a {111} crystal face.
The spinel type lithium ion battery anode active material provided by the invention is of a micro-nano hierarchical porous structure, and the micro-nano hierarchical porous structure is more favorable for electrolyte infiltration and lithium ion rapid transmission, so that a higher active substance utilization rate is ensured in a discharging process, and the lithium ion battery is ensured to have high energy density and excellent rate capability.
LiNi which is a spinel phase positive electrode active material at present0.5Mn1.5O4The cycle performance, especially the cycle performance at higher current density, is poor, mainly due to the dissolution of Mn in the material and Mn3+The resulting Jahn-Teller distortion effect causes structural degradation. Aiming at the defects of the prior art, the spinel type lithium ion battery anode active material provided by the invention is prepared from a plurality of orthogonal LiNi0.5Mn1.5O4A plurality of LiNi0.5Mn1.5O4The dominant exposed crystal face of the nano sheet is a {111} crystal face and a spinel phase LiNi0.5Mn1.5O4The {111} crystal face of the positive active material is more stable relative to other crystal faces, and Mn is most difficult to dissolve out on the {111} crystal face, so that the dissolution of Mn can be limited to the greatest extent fundamentally by using the positive active material provided by the invention, and the excellent long-cycle performance and the rapid charge/discharge performance of the lithium ion battery are ensured.
The invention also provides a preparation method of the spinel type lithium ion battery anode active material, which comprises the following steps:
s1: dissolving hexamethylenetetramine in a mixed solvent; the mixed solvent consists of diethylene glycol and deionized water;
s2: sequentially adding manganese acetate and nickel acetate into the mixed solvent, stirring until the manganese acetate and the nickel acetate are completely dissolved, pouring the obtained mixed solution into a hydrothermal kettle for solvent thermal reaction to obtain a precursor;
s3: adding lithium acetate and the precursor into absolute ethyl alcohol, stirring and evaporating to dryness, and sintering to obtain the spinel type lithium ion battery anode active material LiNi0.5Mn1.5O4。
The preparation method of the spinel type lithium ion battery anode active material provided by the invention comprises the following steps of firstly, selecting hexamethylenetetramine as a precipitator and mixed liquid of diethylene glycol and deionized water as a solvent; then adding manganese acetate and nickel acetate into the mixed solvent for dissolvingThen carrying out a solvothermal reaction, wherein in the solvothermal reaction, the mixed solvent of diethylene glycol and deionized water has high steric hindrance effect, can effectively prevent primary crystal nuclei from approaching each other, and simultaneously, hexamethylenetetramine as a precipitator is heated to slowly decompose to generate CO2Mn in manganese acetate and nickel acetate2+、Ni2+With CO2Carbonate precipitate (namely precursor) is generated by the reaction, and the hexamethylene tetramine can be slowly decomposed to generate CO2So that the precipitation reaction of the manganese acetate and the nickel acetate can be slowly carried out, and the obtained carbonate precipitate has uniform size and shape; in addition, diethylene glycol molecules can be preferentially adsorbed on a certain crystal face of the carbonate precipitate, so that Gibbs free energy of the crystal face is reduced, crystal grains can grow along the specific crystal face, and the formation of an orthogonal nanosheet structure is facilitated; and finally, uniformly distributing lithium acetate on the carbonate precipitate through absolute ethyl alcohol, evaporating the absolute ethyl alcohol, and then sintering to obtain the spinel type lithium ion battery anode active material with good crystallinity and no other impurity phases. The preparation method provided by the invention has the advantages of simple process and low cost, and the prepared anode active material is of a micro-nano hierarchical porous structure and is prepared from a plurality of orthogonal LiNi0.5Mn1.5O4A plurality of said LiNi0.5Mn1.5O4The dominant exposed crystal face of the nanosheet is a {111} crystal face, and when the positive active material is used in a lithium ion battery, the lithium ion battery has high energy density, excellent rate capability, excellent long-cycle performance and rapid charge/discharge performance.
Preferably, the molar ratio of the manganese acetate to the nickel acetate to the lithium acetate is 3: 1: 2.1, taking into account the volatilization loss of lithium during sintering, the proportion of manganese, nickel and lithium is in accordance with LiNi0.5Mn1.5O4Based on the stoichiometric ratio of the elements, the lithium is excessive by 5 percent.
Preferably, in step S1, the volume ratio of the diethylene glycol to the deionized water in the mixed solvent is 1:1, the generation of an orthogonal nanosheet structure is facilitated.
Preferably, in step S1, the concentration of hexamethylenetetramine after the hexamethylenetetramine is dissolved in the mixed solvent is 0.2 mol/L. Too little hexamethylenetetramine can lead to incomplete precipitation reactions; while too much hexamethylenetetramine reduces the solubility of the solvent, which is detrimental to the formation of a homogeneous product, and a suitable amount of hexamethylenetetramine as a precipitant helps to achieve uniform nucleation.
Preferably, in step S2, the temperature of the solvothermal reaction is 160-200 ℃ and the time is 24 h. Wherein the reaction temperature is preferably 180 ℃, which is favorable for the complete decomposition of the hexamethylenetetramine to form CO2And simultaneously, the uniform generation of carbonate precipitate is facilitated.
Preferably, in step S3, the addition amount of the absolute ethyl alcohol is 50-60 mL, so as to facilitate the dispersion of the lithium acetate and the precursor, and thus facilitate the uniform dispersion of the lithium acetate on the precursor, and compared with mechanical mixing, the dispersion of the lithium acetate in the invention is more uniform.
Preferably, in step S3, the stirring is performed until the absolute ethyl alcohol is evaporated to dryness at room temperature by magnetic stirring, and the rotation speed is 2000 r/min. Stirring and evaporating to dryness to facilitate the lithium acetate to be uniformly dispersed on the precursor.
Preferably, in step S3, the sintering process specifically includes:
heating the sintering temperature from room temperature to 400 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 5 hours;
heating the sintering temperature from 400 ℃ to 750 ℃ at the heating rate of 3 ℃/min, and preserving the heat for 6 h.
And the segmented sintering is beneficial to maintaining the orthogonal nanosheet structure.
Preferably, the sintering is carried out in an air atmosphere, and the carbonate precursor is decomposed to produce CO during the air sintering process2The gas can form a porous structure, which is beneficial to the infiltration of electrolyte and the rapid transmission of lithium ions.
Example 1
The embodiment provides a preparation method of a spinel type lithium ion battery positive electrode active material, which comprises the following steps:
s1: dissolving 1.96g of hexamethylenetetramine in 70ml of mixed solvent, and stirring at normal temperature until the solution is clear; the mixed solvent consists of diethylene glycol and deionized water in a volume ratio of 1: 1;
s2: 2.75g of Mn (CH)3COO)2·4H2O and 0.93g Ni (CH)3COO)2·4H2Adding O into the mixed solvent in sequence, stirring at normal temperature until the O is completely dissolved, pouring the obtained mixed solution into a hydrothermal kettle, and preserving heat at 180 ℃ for 24 hours to obtain a precursor;
s3: 0.8g of CH3COOLi·2H2Adding O and the precursor into 60mL of absolute ethyl alcohol, magnetically stirring at room temperature of 2000r/min until the absolute ethyl alcohol is evaporated to dryness, placing a sample obtained by evaporation to dryness in a ceramic crucible and placing the ceramic crucible at the central position of a muffle furnace, firstly heating to 400 ℃ at the heating rate of 1 ℃/min and preserving heat for 5 hours under the air atmosphere, then heating to 750 ℃ at the heating rate of 3 ℃/min and preserving heat for 6 hours, and naturally cooling to room temperature to obtain the spinel type lithium ion battery anode active material LiNi0.5Mn1.5O4。
FIG. 1 shows LiNi, a positive electrode active material of a spinel-type lithium ion battery prepared in this example0.5Mn1.5O4As can be seen from fig. 1, the prepared cathode material has a spinel structure, high crystallinity, and good matching between the peak position and the XRD standard card, and has no impurity peak.
FIGS. 2a and 2b are SEM pictures of the precursor prepared in this example at different magnifications, and FIGS. 2c and 2d are LiNi prepared in this example0.5Mn1.5O4SEM pictures at different magnifications. As can be seen from FIGS. 2a and 2b, the precursor has a uniform morphology and a mean diameter of about 4-5 μm, and is assembled from a plurality of orthogonal nanosheets. The precursor is converted into LiNi through a high-temperature sintering recrystallization process0.5Mn1.5O4Then, the micro-morphology of the precursor is retained, and a micro-nano hierarchical porous structure assembled by orthogonal nano sheets is formed (fig. 2c and 2 d).
FIG. 3 shows LiNi, a final product obtained in this example0.5Mn1.5O4Further demonstrating the LiNi prepared in this example0.5Mn1.5O4The material has a micro-nano hierarchical porous structure and is composed of a plurality of orthogonal nano-particlesThe rice sheet is assembled, the dominant exposed crystal face of the nano sheet is a {111} crystal face, and LiNi is0.5Mn1.5O4The thickness of the nano sheet is 50-100 nm.
FIG. 4 shows LiNi prepared in this example0.5Mn1.5O4As can be seen from the element distribution picture of the material, three elements of Mn, Ni and O are uniformly distributed in an orthogonal nanosheet structure LiNi0.5Mn1.5O4In the material.
FIG. 5 shows LiNi prepared in this example0.5Mn1.5O4And (3) a cycle performance curve diagram of the lithium ion battery as the anode. As can be seen from the figure, the first discharge capacity of the electrode is 112mAh/g under the discharge current density of 20C, after 500 charge-discharge cycles, the discharge capacity is kept at 93mAh/g, the capacity retention rate is 83%, and the LiNi with the orthogonal nanosheet structure is disclosed0.5Mn1.5O4The lithium ion battery positive electrode has excellent cycle performance.
FIG. 6 shows LiNi prepared in this example0.5Mn1.5O4And the performance diagram is used as the rate capability diagram of the lithium ion battery of the positive electrode. As can be seen from the graph, the positive electrode material showed that the capacity fading was not significant at the discharge current densities of 1C, 2C, 5C, 10C, 20C, 30C, and 40C, and the capacity was restored to the initial value even when the discharge current was restored to 1C, indicating that the orthogonal nanosheet-structured LiNi0.5Mn1.5O4The lithium ion battery anode has excellent rate performance, and further explains the key effect of crystal face regulation and structural design on the comprehensive electrochemical performance of the lithium ion battery.
Example 2
Compared with the embodiment 1, in the embodiment, in the step S2, the precursor is obtained by maintaining the temperature at 160 ℃ for 24 hours. The other steps are the same as in example 1.
The lithium ion battery cathode material LiNi prepared by the embodiment0.5Mn1.5O4The microstructure of the nano-porous structure is similar to that of the micro-nano hierarchical porous structure in the embodiment 1, and the nano-porous structure is composed of a plurality of orthogonal nano-sheetsLiNi0.5Mn1.5O4A material.
Example 3
Compared with the embodiment 1, in the step S2 of the embodiment, the precursor is obtained by maintaining the temperature at 200 ℃ for 24 hours. The other steps are the same as in example 1.
The lithium ion battery cathode material LiNi prepared by the embodiment0.5Mn1.5O4The microstructure of (a) is similar to that in example 1, and the LiNi is a micro-nano hierarchical porous structure and consists of a plurality of orthogonal nano sheets0.5Mn1.5O4A material.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the contents of the present specification and the accompanying drawings, or directly/indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims (8)

1. A preparation method of a spinel type lithium ion battery positive electrode active material is characterized by comprising the following steps:
s1: dissolving hexamethylenetetramine in a mixed solvent; the mixed solvent consists of diethylene glycol and deionized water; the volume ratio of diethylene glycol to deionized water in the mixed solvent is 1: 1;
s2: sequentially adding manganese acetate and nickel acetate into the mixed solvent, stirring until the manganese acetate and the nickel acetate are completely dissolved, pouring the obtained mixed solution into a hydrothermal kettle for solvent thermal reaction to obtain a precursor;
s3: adding lithium acetate and the precursor into absolute ethyl alcohol, stirring and evaporating to dryness, and sintering to obtain the spinel type lithium ion battery anode active material LiNi0.5Mn1.5O4；
The positive active material is in a solid polyhedral shape, is in a micro-nano hierarchical porous structure and is composed of a plurality of orthogonal LiNi0.5Mn1.5O4A nanosheet, aThe LiNi0.5Mn1.5O4The nano sheet is a porous nano sheet, and the porous nano sheet consists of a plurality of nano particles; a plurality of the LiNi0.5Mn1.5O4The dominant exposed crystal face of the nano sheet is a {111} crystal face.
2. The method of claim 1, wherein the molar ratio of manganese acetate, nickel acetate and lithium acetate is 3: 1: 2.1.
3. the method according to claim 1, wherein in step S1, the concentration of hexamethylenetetramine after dissolving hexamethylenetetramine in the mixed solvent is 0.2 mol/L.
4. The method according to claim 1, wherein the solvothermal reaction is performed at 160-200 ℃ for 24 hours in step S2.
5. The method according to claim 1, wherein the absolute ethanol is added in an amount of 50 to 60mL in step S3.
6. The method of claim 1 or 5, wherein in step S3, the stirring and evaporating step is magnetic stirring at room temperature until the absolute ethyl alcohol is evaporated to dryness, and the rotation speed is 2000 r/min.
7. The method according to claim 1 or 5, wherein in step S3, the sintering process is specifically:
heating the sintering temperature from room temperature to 400 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 5 hours;
heating the sintering temperature from 400 ℃ to 750 ℃ at the heating rate of 3 ℃/min, and preserving the heat for 6 h.
8. The method of claim 7, wherein the sintering is performed in an air atmosphere.
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Title
"Constructing hierarchical urchin-like LiNi0.5Mn1.5O4 hollow spheres with exposed {111} facets as advanced cathode material for lithium-ion batteries";Weiwei Sun等;《Nano Energy》;20181010;第54卷;第175-183页 *
"Hierarchical waxberry-like LiNi0.5Mn1.5O4 as an advanced cathode material for lithium-ion batteries with a superior rate capability and long-term cyclability";Weiwei Sun等;《J. Mater. Chem. A》;20180622;第6卷;第14155页 *

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