CN117059780A - Rectangular laminated hollow spherical secondary battery anode material and preparation method and application thereof - Google Patents
Rectangular laminated hollow spherical secondary battery anode material and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000010405 anode material Substances 0.000 title claims abstract description 16
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 23
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 22
- 239000011029 spinel Substances 0.000 claims abstract description 22
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- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims abstract description 8
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 8
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- 239000002033 PVDF binder Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
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- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/04—Processes of manufacture in general
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
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- 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 belongs to the technical field of new energy materials, and particularly relates to a cuboid laminated hollow spherical secondary battery anode material, a preparation method and application thereof, wherein the chemical formula of the cuboid laminated hollow spherical spinel type high-entropy oxide is M 3 O 4 Wherein M is at least five of Cr, mn, fe, co, ni, zn, mg; the shape is a cuboid laminated hollow sphere, wherein the cuboid consists of a plurality of tiny nano particles; the preparation method comprises the steps of adopting metal sulfate as a metal source, urea as a precipitator and dodecyl trimethyl ammonium bromide as a surfactant, precisely regulating and controlling the interaction among the raw materials, and preparing the catalyst by a hydrothermal method and a solid phase reaction methodThe spinel type high-entropy oxide secondary battery anode material with the special microstructure and the equal molar ratio. The electrochemical performance, particularly the multiplying power performance, of the battery anode material is obviously improved, and the preparation method has the advantages of simple flow, mild reaction conditions and environment-friendly reaction process.
Description
Technical Field
The invention belongs to the technical field of new energy materials, and particularly relates to a cuboid laminated hollow spherical secondary battery anode material, and a preparation method and application thereof.
Background
In recent years, a new class of materials with complex stoichiometric ratios, namely High Entropy Oxides (HEOs), are increasingly in the brand-new corner of the electrochemical energy storage field. Compared with the traditional doped transition metal oxide, the method has the following advantages: 1) Highly disordered and distorted lattices, which are prone to create a large number of intrinsic defects in the material, such as high concentrations of oxygen vacancies and lattice distortions, can promote enhanced ion and electron transfer; 2) The HEO can maintain the structural stability even under extreme conditions due to the thermodynamic high entropy effect and the kinetic delayed diffusion effect, so that the cycle performance can be improved; 3) The abundant and flexible component design can reduce the lazy property of single element, such as expensive Co element, and provide a new way for customizing and regulating electrode materials; 4) The introduction of multiple elements or the change of stoichiometric ratio not only can regulate and control electron distribution, but also can control the Fermi level related to electrode potential; a synergistic effect between groups of members may also be achieved.
Spinel-type HEOs not only have higher theoretical specific capacity, but also spinel AB 2 O 4 The structure has three-dimensional Li + The random distribution of the diffusion channel, cations at the two Wyckoff sites (8 b and 16 c), will further enhance the conformational entropyAnd forms mixed valence state, which is beneficial to increasing the concentration of oxygen vacancies in the electrode material and improving the speed and quantity of electron transmission. At present, a spinel type HEOs (high-temperature solid phase) method is mainly adopted for preparing micron-sized powder materials, and in order to improve the lithium ion storage performance, a solution combustion method, a coprecipitation method and a hydrothermal method are used for preparing spinel type HEOs nano powder, and although the spinel type HEOs nano powder shows stable reversible capacity in a long-term circulation process, most of nano powder materials have obvious capacity loss in a front-stage circulation process, so that the practical application of the existing high-entropy oxide is prevented.
To improve the early-stage circulation stability, the product of the oxidation treatment of CoCrFeMnNi as a raw material was prepared by the method of Xiao et al (Co 0.2 Cr 0.2 Fe 0.2 Mn 0.2 Ni 0.2 ) 3 O 4 High entropy oxide, HEOs particles are micron-sized particles composed of a plurality of nanoparticles, the negative electrode material of the specific microstructure is prepared by a high temperature solid phase method (Co 0.2 Cr 0.2 Fe 0.2 Mn 0.2 Ni 0.2 ) 3 O 4 The negative electrode material shows more excellent specific capacity, rate capability and cycle stability, and after 2.0A/G cycle of 1200 cycles, a high reversible capacity of 596.5 mA.h/G and a capacity retention of 86.2% are obtained (Xiao B, wu G, wang T, et al high-entropy oxides as advanced anode materials for long-life lithium-ion Batteries [ J ]]Nano Energy,2022,95 (none): 106962.). However, the method has complex process and high cost. Therefore, how to further improve the early-stage cycling stability of spinel-type HEOs negative electrode materials by improving the preparation method is a problem to be solved in the art.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a cuboid laminated hollow spherical secondary battery anode material, and a preparation method and application thereof.
In order to achieve the technical purpose and the technical effect, the invention is realized by the following technical scheme:
the invention provides a cuboid laminated hollow spherical secondary battery anode materialThe chemical formula of the material is M 3 O 4 Wherein M is at least five of Cr, mn, fe, co, ni, zn, mg; the crystal structure of the material is spinel; the shape of the material is a cuboid laminated hollow sphere, wherein the cuboid consists of a plurality of nano particles.
The invention also provides a preparation method of the cuboid laminated hollow spherical secondary battery anode material, which comprises the following steps:
1) According to formula M 3 O 4 Weighing metal sulfate with stoichiometric ratio, dissolving in distilled water, and stirring uniformly to obtain mixed solution of metal sulfate;
2) Weighing a certain amount of precipitant and surfactant, adding into the mixed solution of the metal sulfate obtained in the step 1), and uniformly stirring;
3) Transferring the mixed solution obtained in the step 2) to a polytetrafluoroethylene lining reaction kettle for hydrothermal reaction, cooling to room temperature, performing suction filtration, washing with deionized water for 2-3 times, and drying to obtain amorphous hydroxide solid powder;
4) And 3) placing the solid powder obtained in the step 3) into a muffle furnace for solid phase reaction to obtain the high-entropy oxide with a single spinel structure.
Further, in the step 1), the concentration of the metal sulfate is 0.075 to 0.1mol/L.
Further, in the step 2), the precipitant is urea, and the molar ratio of the precipitant to the total metal cations in the metal sulfate is 2-4:1.
Further, in the step 2), the surfactant is dodecyl trimethyl ammonium bromide, and the dosage of the surfactant is 0.4-1.0% of the total mass of the mixed solution of the metal sulfate.
Further, in the step 3), the reaction temperature of the hydrothermal reaction is 100-140 ℃ and the reaction time is 3.5-5 h.
Further, in the step 4), the reaction temperature of the solid phase reaction is 350-750 ℃ and the reaction time is 0.5-2 h.
The invention also provides application of the cuboid laminated hollow spherical secondary battery anode material in preparation of a secondary battery anode.
The beneficial effects of the invention are as follows:
1. the raw materials of the invention adopt liquid phase ingredients, so as to ensure that the raw materials reach the molecular level and are uniformly mixed, and the final product realizes the stoichiometric ratio.
2. The invention adopts metal sulfate as a metal source, urea as a precipitator and dodecyl trimethyl ammonium bromide as a surfactant, the interaction between the three is easy to control and prepare the high-entropy oxide anode material with a special structure (a cuboid laminated hollow sphere), and the element content test shows that the proportion of the contained elements is close to equimolar.
3. The preparation method provided by the invention has the advantages of simple flow, mild reaction conditions and environment-friendly reaction process.
4. The preparation method provided by the invention has wide universality for spinel type high-entropy oxides with different chemical compositions.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows a structure of a hollow sphere spinel type (Co) having a rectangular parallelepiped stacked structure prepared in example 1 0.2 Cr 0.2 Fe 0.2 Mn 0.2 Ni 0.2 ) 3 O 4 SEM image of high entropy oxide at first magnification;
FIG. 2 shows a structure of a hollow sphere spinel type (Co) having a rectangular parallelepiped stacked structure prepared in example 1 0.2 Cr 0.2 Fe 0.2 Mn 0.2 Ni 0.2 ) 3 O 4 SEM image of the high entropy oxide at second magnification;
FIG. 3 shows a structure of a hollow sphere spinel type (Co) having a rectangular parallelepiped stacked structure prepared in example 1 0.2 Cr 0.2 Fe 0.2 Mn 0.2 Ni 0.2 ) 3 O 4 SEM image of high entropy oxide at third magnification;
FIG. 4 shows a structure of a hollow sphere spinel type (Co) having a rectangular parallelepiped stacked structure prepared in example 1 0.2 Cr 0.2 Fe 0.2 Mn 0.2 Ni 0.2 ) 3 O 4 XRD pattern of high entropy oxide;
FIG. 5 shows a structure of a hollow sphere spinel type (Co) having a rectangular parallelepiped stacked structure prepared in example 1 0.2 Cr 0.2 Fe 0.2 Mn 0.2 Ni 0.2 ) 3 O 4 The cycle performance and coulombic efficiency of the high entropy oxide negative electrode material at a current density of 2A/g are schematically shown.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention takes metal sulfate as a metal source, urea as a precipitator and dodecyl trimethyl ammonium bromide as a surfactant, and prepares the cuboid laminated hollow spherical spinel M by accurately regulating and controlling the concentration of the metal sulfate, the action between sulfate and the surfactant, adopting a hydrothermal method and by means of high-temperature mutual reaction 3 O 4 High entropy oxide secondary battery negative electrode material.
Specific embodiments of the invention are as follows:
example 1
The preparation method of the cuboid laminated hollow spherical spinel type high-entropy oxide anode material comprises the following steps:
according to the formula (Co) 0.2 Cr 0.2 Fe 0.2 Mn 0.2 Ni 0.2 ) 3 O 4 Corresponding metal sulfate is weighed according to the stoichiometric ratio of the metal sulfate, and specifically: 0.4366g of Co (NO) 3 ) 2 ·6H 2 O, 0.6002g of Cr (NO) 3 ) 3 ·9H 2 O, 0.6060g of Fe (NO) 3 ) 3 ·9H 2 O, 0.3765g of Mn (NO 3 ) 2 ·4H 2 O and 0.4362g of Ni (NO) 3 ) 2 ·6H 2 O, dissolving in 20mL of distilled water, and uniformly stirring at room temperature to obtain a mixed solution containing metal nitrate; then adding 1.3514g of urea and 0.2381g of dodecyl trimethyl ammonium bromide, and stirring uniformly at room temperature; transferring the mixed solution into a polytetrafluoroethylene-lined reaction kettle, performing hydrothermal reaction for 4 hours at 140 ℃, cooling to room temperature, performing suction filtration, washing with deionized water for 3 times, and drying to obtain amorphous hydroxide solid powder; finally, the powder is put into a muffle furnace and heated to 750 ℃ for high-temperature solid-phase reaction for 1h, thus obtaining (Co) 0.2 Cr 0.2 Fe 0.2 Mn 0.2 Ni 0.2 ) 3 O 4 High entropy oxide.
SEM's (FIGS. 1-3) at different magnifications confirm that the prepared high entropy oxide has a rectangular parallelepiped stacked hollow sphere spinel type high entropy oxide. XRD spectra (FIG. 4) showed that the prepared (Co 0.2 Cr 0.2 Fe 0.2 Mn 0.2 Ni 0.2 ) 3 O 4 The high entropy oxide has a single spinel structure.
Preparation of a negative electrode piece and preparation of a lithium ion battery:
the prepared sample is used as an active substance, super P carbon black is used as a conductive agent, polyvinylidene fluoride (PVDF) is used as an adhesive (mass ratio is 7:2:1), and the active substance is dissolved in N-methyl pyrrolidone to prepare slurry which is uniformly coated on a clean copper foil to prepare an electrode plate; then taking a pure lithium sheet as an anode, taking a polypropylene porous membrane as a diaphragm, and lmol/L LiPF 6 The DMC-EC-DEC (volume ratio 1:1:1) solution was used as an electrolyte, and the CR2025 type button cell was assembled in a glove box.
The charge and discharge experiments of the battery were performed on a new battery test system, and the results are shown in fig. 5: (Co) 0.2 Cr 0.2 Fe 0.2 Mn 0.2 Ni 0.2 ) 3 O 4 The electrode is subjected to charge-discharge cycle test under the current density of 2A/g, and the specific capacity of the electrode is 443mAh/g after 1000 cycles within the voltage range of 0.01-3.0V.
Example 2
The preparation method of the cuboid laminated hollow spherical spinel type high-entropy oxide anode material comprises the following steps:
according to the formula (Zn) 0.2 Cr 0.2 Fe 0.2 Mn 0.2 Ni 0.2 ) 3 O 4 Corresponding metal sulfate is weighed according to the stoichiometric ratio of the metal sulfate, and specifically: 0.4462g of Zn (NO) 3 ) 2 ·6H 2 O, 0.6002g of Cr (NO) 3 ) 3 ·9H 2 O, 0.6060g of Fe (NO) 3 ) 3 ·9H 2 O, 0.3765g of Mn (NO 3 ) 2 ·4H 2 O and 0.4362g of Ni (NO) 3 ) 2 ·6H 2 O, dissolving in 15mL of distilled water, and uniformly stirring at room temperature to obtain a mixed solution containing metal nitrate; then adding 1.8018g of urea and 0.0988g of dodecyl trimethyl ammonium bromide, and stirring uniformly at room temperature; transferring the mixed solution into a polytetrafluoroethylene-lined reaction kettle, performing hydrothermal reaction at 120 ℃ for 3.5 hours, cooling to room temperature, performing suction filtration, washing with deionized water for 3 times, and drying to obtain amorphous hydroxide solid powder; finally, the powder is put into a muffle furnace and heated to 350 ℃ for high-temperature solid-phase reaction for 2 hours, thus obtaining (Zn) 0.2 Cr 0.2 Fe 0.2 Mn 0.2 Ni 0.2 ) 3 O 4 High entropy oxide.
Preparation of a negative electrode piece and preparation of a lithium ion battery:
the prepared sample is used as an active substance, super P carbon black is used as a conductive agent, polyvinylidene fluoride (PVDF) is used as an adhesive (mass ratio is 7:2:1), and the active substance is dissolved in N-methyl pyrrolidone to prepare slurry which is uniformly coated on a clean copper foil to prepare an electrode plate; then taking a pure lithium sheet as an anode, taking a polypropylene porous membrane as a diaphragm, and lmol/L LiPF 6 DMC-EC-DEC (volume ratio 1:1:1) as electrolyte, and in a glove boxThe CR2025 button cell is assembled.
The charge and discharge experiments of the battery were performed on a new battery test system, and the results were as follows: (Zn) 0.2 Cr 0.2 Fe 0.2 Mn 0.2 Ni 0.2 ) 3 O 4 The electrode is subjected to charge-discharge cycle test under the current density of 2A/g, and the specific capacity of the electrode is 416mAh/g after 1000 cycles within the voltage range of 0.01-3.0V.
Example 3
The preparation method of the cuboid laminated hollow spherical spinel type high-entropy oxide anode material comprises the following steps:
according to the formula (Mg) 1/6 Zn 1/6 Cr 1/6 Fe 1/6 Mn 1/6 Ni 1/6 ) 3 O 4 Corresponding metal sulfate is weighed according to the stoichiometric ratio of the metal sulfate, and specifically: 0.3053g of Mg (NO) 3 ) 2 ·6H 2 O, 0.4462g of Zn (NO) 3 ) 2 ·6H 2 O, 0.6002g of Cr (NO) 3 ) 3 ·9H 2 O, 0.6060g of Fe (NO) 3 ) 3 ·9H 2 O, 0.3765g of Mn (NO 3 ) 2 ·4H 2 O and 0.4362g of Ni (NO) 3 ) 2 ·6H 2 O, dissolving in 20mL of distilled water, and uniformly stirring at room temperature to obtain a mixed solution containing metal nitrate; then adding 1.8919g of urea and 0.2008g of dodecyl trimethyl ammonium bromide, and stirring uniformly at room temperature; transferring the mixed solution into a polytetrafluoroethylene-lined reaction kettle, performing hydrothermal reaction at 100 ℃ for 5 hours, cooling to room temperature, performing suction filtration, washing with deionized water for 3 times, and drying to obtain amorphous hydroxide solid powder; finally, the powder is put into a muffle furnace and heated to 650 ℃ for high-temperature solid-phase reaction for 1.5h, thus obtaining (Mg) 1/6 Zn 1/6 Cr 1/6 Fe 1/6 Mn 1/6 Ni 1/6 ) 3 O 4 High entropy oxide.
Preparation of a negative electrode piece and preparation of a lithium ion battery:
the samples prepared above were used as active material, super P carbon black as conductive agent, polyvinylidene fluoride (PVDF) as binder (mass ratio 7:2:1),dissolving in N-methyl pyrrolidone to prepare slurry, and uniformly coating the slurry on a clean copper foil to prepare an electrode plate; then taking a pure lithium sheet as an anode, taking a polypropylene porous membrane as a diaphragm, and lmol/L LiPF 6 The DMC-EC-DEC (volume ratio 1:1:1) solution was used as an electrolyte, and the CR2025 type button cell was assembled in a glove box.
The charge and discharge experiments of the battery were performed on a new battery test system, and the results were as follows: (Mg) 1/6 Zn 1/6 Cr 1/6 Fe 1/ 6 Mn 1/6 Ni 1/6 ) 3 O 4 The electrode is subjected to charge-discharge cycle test under the current density of 2A/g, and the specific capacity of the electrode is 478mAh/g after 1000 cycles within the voltage range of 0.01-3.0V.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (8)
1. A cuboid laminated hollow sphere secondary battery cathode material is characterized in that: the chemical formula of the material is M 3 O 4 Wherein M is at least five of Cr, mn, fe, co, ni, zn, mg; the crystal structure of the material is spinel; the shape of the material is a cuboid laminated hollow sphere, wherein the cuboid consists of a plurality of nano particles.
2. The method for preparing a rectangular parallelepiped laminated hollow sphere secondary battery anode material according to claim 1, comprising the steps of:
1) According to formula M 3 O 4 Weighing metal sulfate with stoichiometric ratio, dissolving in distilled water, and stirring to obtain mixed solution of metal sulfate；
2) Weighing a certain amount of precipitant and surfactant, adding into the mixed solution of the metal sulfate obtained in the step 1), and uniformly stirring;
3) Transferring the mixed solution obtained in the step 2) to a polytetrafluoroethylene lining reaction kettle for hydrothermal reaction, cooling to room temperature, performing suction filtration, washing with deionized water for 2-3 times, and drying to obtain amorphous hydroxide solid powder;
4) And 3) placing the solid powder obtained in the step 3) into a muffle furnace for solid phase reaction to obtain the high-entropy oxide with a single spinel structure.
3. The preparation method according to claim 2, characterized in that: in the step 1), the concentration of the metal sulfate is 0.075-0.1 mol/L.
4. The preparation method according to claim 2, characterized in that: in the step 2), the precipitant is urea, and the molar ratio of the precipitant to the total metal cations in the metal sulfate is 2-4:1.
5. The preparation method according to claim 2, characterized in that: in the step 2), the surfactant is dodecyl trimethyl ammonium bromide, and the dosage of the surfactant is 0.4-1.0% of the total mass of the mixed solution of the metal sulfate.
6. The preparation method according to claim 2, characterized in that: in the step 3), the reaction temperature of the hydrothermal reaction is 100-140 ℃ and the reaction time is 3.5-5 h.
7. The preparation method according to claim 2, characterized in that: in the step 4), the reaction temperature of the solid phase reaction is 350-750 ℃ and the reaction time is 0.5-2 h.
8. The use of the rectangular parallelepiped laminated hollow sphere secondary battery anode material according to claim 1 for preparing a secondary battery anode.
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