CN111048765B - Preparation method of battery composite electrode material - Google Patents

Preparation method of battery composite electrode material Download PDF

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CN111048765B
CN111048765B CN201911376208.2A CN201911376208A CN111048765B CN 111048765 B CN111048765 B CN 111048765B CN 201911376208 A CN201911376208 A CN 201911376208A CN 111048765 B CN111048765 B CN 111048765B
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electrode material
tin
simple substance
graphite
phosphorus
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CN111048765A (en
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孙黎
张元星
张以河
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China University of Geosciences Beijing
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China University of Geosciences Beijing
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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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • Y02E70/00—Other energy conversion or management systems reducing GHG emissions
    • Y02E70/30—Systems combining energy storage with energy generation of non-fossil origin

Abstract

The invention provides a preparation method of a battery composite electrode material. The preparation method of the battery composite electrode material comprises the following steps: mixing the phosphorus simple substance, the tin simple substance and the graphite, and performing ball milling under the inert gas atmosphere to obtain the composite material. Wherein, the ball milling is high-energy ball milling, and the rotating speed is preferably 100 r/min-900 r/min. The method provided by the invention can uniformly disperse the three components by ball milling, and the obtained composite electrode material is used as an electrode material of a lithium ion battery and a sodium ion battery. Compared with the traditional phosphide or red phosphorus composite synthesis method, the method is more convenient and faster, the prepared material has certain pores on the surface, but has dispersibility, and has the advantages of convenience, environmental protection, cleanness and the like in the production process of the material. The composite electrode material obtained by the invention shows excellent specific capacity, charge-discharge cycle stability and rate capability as the electrode material of lithium ion batteries and sodium ion batteries.

Description

Preparation method of battery composite electrode material
Technical Field
The invention relates to the field of composite materials, in particular to a preparation method of a battery composite electrode material.
Background
A rechargeable battery having excellent performance is extremely important for use of renewable energy sources such as new energy vehicles and solar and wind energy. For a new energy automobile, a battery with large electric capacity and high output power can bring sufficient power and endurance for the new energy automobile; for the utilization of renewable energy sources such as solar energy and wind energy, a large-scale energy source is requiredThe excellent electric energy storage device stores the energy so as to smoothly supply the energy to the grid, otherwise the energy cannot be fully utilized. Alkali metal ion (Li)+/Na+) Batteries are one of the emerging candidate systems for power grid energy storage due to their inherent safety, and researchers have made some preliminary investigations on the battery system in early studies.
In recent years, lithium ion batteries and sodium ion batteries have received more and more attention due to the advantages of abundant lithium/sodium resource reserves, wide distribution, low cost and the like. The lithium ion battery is a new generation of rechargeable battery following the conventional storage battery such as nickel hydrogen, and was first developed and succeeded by the japanese sony corporation in 1990. The lithium ion battery has simple working principle, better safety and longer charge-discharge service life, and is considered as the first choice of a novel power source. Lithium ion batteries have the following advantages. The operating voltage is high. The discharge voltage of one lithium ion battery is equivalent to 3 traditional storage batteries, and the battery usage amount is greatly reduced under the same use condition. The energy density is high. 2 to 3 times of the common storage battery, small volume and light weight. The cycle life is long. The service life of the battery is as long as 10-15 years, and compared with the traditional battery for 7-8 years, the battery reduces the influence caused by high cost. No environmental pollution. It contains no lead, mercury and other heavy metals, and is a clean green energy source. Has no memory effect. Can be charged and discharged at will, particularly shows excellent service performance in wartime and emergency, hardly needs any maintenance, and has the advantages of high safety performance, wide working temperature range and the like. Meanwhile, the alkali metal battery can also use other metals as a positive electrode.
Sodium is ubiquitous in the ocean and available in quantities thousands of times as much as lithium, making sodium metal batteries more popular with scientists than lithium batteries. Compared with sodium ion batteries, metal sodium batteries have sufficiently high voltage, long cycle life and fast charge and discharge rates. Sodium metal batteries are therefore considered as one of the new generation battery systems replacing lithium batteries. However, since sodium ions have a large ionic radius (sodium ions: 0.98A and lithium ions: 0.69A), the kinetic process is slow, and the electrochemical properties are difficult to satisfy the practical application requirements. Therefore, the search for electrode materials for high capacity long cycle life sodium ion batteries is one of the key to the development of sodium ion batteries. Among a plurality of negative electrode materials, red phosphorus gradually develops as a key point of negative electrode material research due to the advantages of extremely high theoretical specific capacity (2595 mAh/g), low price, environmental friendliness and the like. However, when used in lithium ion batteries and sodium ion batteries, the red phosphorus has low electron conductivity and large volume change during cycling, so that the lithium and sodium storage properties of the red phosphorus are rapidly deteriorated.
Some novel carbon-based materials (carbon nano tubes, carbon spheres, graphene, graphite and the like) with special structures can be used as reinforcing materials to be compounded with active electrode materials of lithium ion batteries and sodium ion batteries, so that the conductivity is enhanced, and the rate capability of samples is improved. However, for the combination with the simple substance, the particle size of the simple substance tin and the simple substance red phosphorus is larger. Such an electrode material that can have the preferable properties as described above has not been provided in the prior art for a long time.
Disclosure of Invention
In order to solve the problems of unstable structure, large particle size, low conductivity, short life cycle, poor specific capacity, poor rate capability and the like of the existing tin phosphide electrode material, the first purpose of the invention is to provide a preparation method of a battery composite electrode material, which comprises the following steps: mixing the phosphorus simple substance, the tin simple substance and the graphite, and performing ball milling under the inert gas atmosphere to obtain the composite material.
In the prior art, simple mechanical mixing can cause the layering of a tin simple substance, a phosphorus simple substance and a carbon material, the electrochemical performance of the material is poor due to no substantial change, ball milling, particularly high-energy ball milling, is a fully dispersed reactor, the method can fully disperse, reduce the particle size, increase the surface energy and increase lithium/sodium storage active sites, but if the high-energy ball milling is carried out on carbon nanotubes and graphene, an inventor does not obtain good effect through multiple experiments, in fact, under the high-energy ball milling, the sheet structure of the graphene and the tubular structure of the carbon nanotubes are damaged,the active material cannot be protected from the electrochemical performance. In the selection of the carbon material under the high-energy ball milling, graphite with lower price and thicker lamella is used. The graphite has good conductivity, high crystallinity and good layered structure, and is very suitable for the intercalation and deintercalation of lithium ions. And lithium forms LiC after intercalation into graphite6The structure of (2) has high charge-discharge efficiency and working voltage. And the graphite has good toughness, and can relieve volume expansion of tin and phosphorus and prevent pulverization of phosphorus-tin particles by forming a composite electrode with the metal tin and the phosphorus.
The method provided by the invention can uniformly disperse the three components by high-energy ball milling, and the obtained composite electrode material is used as an electrode material of a lithium ion battery and a sodium ion battery. Compared with the traditional phosphide or red phosphorus composite synthesis method, the method is more convenient and faster, the prepared material has certain pores on the surface, has dispersibility, has the advantages of convenience, environmental protection, cleanness and the like in the production process of the material, and is an extremely excellent inorganic material synthesis method with low energy consumption. The phosphorus simple substance and the tin simple substance of the battery composite material obtained by the preparation method of the invention are subjected to high-energy ball milling to reduce the particle size, and the crystallinity is not influenced. The method is simple and easy to implement and low in cost, and the obtained composite material as an electrode material of a lithium ion battery and a sodium ion battery shows excellent specific capacity, charge-discharge cycle stability and rate capability. In the embodiment of the present invention, the elemental phosphorus is preferably elemental red phosphorus. In a particular embodiment of the invention, the graphite is preferably flake graphite (microscopic). In the present invention, the elemental phosphorus, the elemental tin, and the graphite are preferably mixed in a powdery form (macroscopically). Wherein, graphite is preferably 3000-4000 meshes.
In a preferred embodiment of the present invention, the molar ratio of the phosphorus simple substance to the tin simple substance is 1:5 to 5:1, and preferably (1 to 5): 4, more preferably (3-4): 4.
In a preferred embodiment of the invention, the adding amount of the graphite is 1:1 to 1:9, preferably 1:1 to 1:5, and more preferably 1:1.5 to 1:3 of the total mass of the phosphorus simple substance and the tin simple substance.
In a preferred embodiment of the present invention, the ball-milling ratio of balls to materials is 20:1 to 150:1, preferably 50:1 to 130:1, and more preferably 70:1 to 80: 1.
In a preferred embodiment of the invention, the rotation speed of the ball mill is 100r/min to 900r/min, preferably 200r/min to 700r/min, and more preferably 300r/min to 400 r/min.
In a preferred embodiment of the present invention, the ball milling time is 5 to 50 hours, preferably 15 to 45 hours, and more preferably 30 to 40 hours.
In the invention, the ball milling is carried out in a ball milling tank, and the material of the ball milling tank comprises but is not limited to stainless steel material, and can be agate, zirconium dioxide and other materials which can not generate chemical reaction with reactants under a high energy state. The ball milling medium can be one or more of stainless steel grinding beads, agate balls, zirconium dioxide balls and other mediums with stable phases, and the diameter of the ball milling medium is 0.1-0.5 cm.
In a preferred embodiment of the present invention, a method for preparing a composite electrode material for a battery includes the steps of: mixing a red phosphorus simple substance, a tin simple substance and graphite, and carrying out ball milling for 5-50 h at the rotating speed of 100-900 r/min in an inert gas atmosphere to obtain the red phosphorus simple substance; the molar ratio of the red phosphorus simple substance to the tin simple substance is 1: 5-5: 1; the adding amount of the graphite is 1: 1-1: 9 of the total mass of the red phosphorus simple substance and the tin simple substance; the ball-material ratio of the ball milling is 20: 1-150: 1.
The inert gas of the present invention may be argon or nitrogen.
The battery composite electrode material obtained by the preparation method is a phosphorus-tin @ graphite composite electrode material, the material has a micro-nano structure with components having monodispersity and mutually connected, and certain nano pores are formed on the surfaces of phosphorus and tin. After the graphite is added into the stone mill and reacts, the structure of the graphite is not damaged by the high-energy ball milling, the chemical combination reaction of phosphorus and tin is prevented, and the graphite is used as an intercalation to provide a bridge for the synergistic action of the phosphorus and the tin, the graphite is tightly combined on the surfaces of the graphite and the graphite, and the synergistic action of the phosphorus and the tin improves the electron transmission efficiency and the ion transmission efficiency of the material.
Namely, another object of the present invention is to provide a battery composite electrode material obtained by the above-mentioned preparation method. Among them, the battery of the present invention is preferably a lithium ion battery or a sodium ion battery.
The invention further aims to provide the application of the preparation method or the battery composite electrode material obtained by the preparation method in the electrode material of the lithium ion battery and/or the sodium ion battery. The composite electrode material of the battery can effectively improve the charge-discharge cycle stability and rate capability of the battery, in particular to a lithium ion battery and a sodium ion battery.
The preparation method is simple, after the graphite is added when the elemental phosphorus and the elemental tin are mixed, the elemental phosphorus and the elemental tin can be prevented from generating a tin phosphide phase with poor electrochemical performance under high-energy ball milling, the original elemental state is kept, the particle size is reduced, the active position where lithium ions and sodium ions are inserted is greatly increased, and the conductivity is increased. Compared with the existing method that the phosphorus simple substance and tin are firstly ball-milled to obtain tin phosphide and then graphite is added to obtain the cathode material, the method only adopts the mixture of the three simple substances, and phase tin phosphide with poor electrochemical performance is not generated. Meanwhile, the method provided by the invention obviously improves and improves the charge-discharge cycle stability and rate capability of the lithium ion battery and the sodium ion battery.
Drawings
FIG. 1 is an XRD plot of pure tin phosphide electrode materials prepared in examples 1-5 and comparative example 1, and a carbon content gradient P-Sn @ G.
Fig. 2 is an SEM image of graphite used in the examples.
FIG. 3 is an SEM photograph of red phosphorus used in examples.
FIG. 4 is pure tin phosphide (Sn) prepared in comparative example 14P3) SEM image of electrode material.
FIG. 5 is an SEM image of the P-Sn @ G73 composite electrode material prepared in example 1.
FIG. 6 is an EDX energy spectrum of the P-Sn @ G73 composite electrode material prepared in example 1.
FIG. 7 Transmission Electron microscopy of a P-Sn @ G73 composite electrode material prepared in example 1.
FIG. 8 is a plot of constant current discharge at different scan rates of the P-Sn @ G73 composite electrode material prepared in example 1 as a half-cell of a lithium ion battery.
FIG. 9 is a graph showing the charge-discharge cycle curves (at 0.2C rate) of the pure tin phosphide electrode materials and the carbon content gradient P-Sn @ G material prepared in examples 1-5 and comparative example 1 as half-cells of lithium ion batteries.
FIG. 10 is a graph showing the rate of change of pure tin phosphide electrode materials and carbon content gradient P-Sn @ G materials prepared in examples 1-5 and comparative example 1 as half-cells of lithium ion batteries.
Fig. 11 is a plot of constant current discharge as a half-cell of a sodium ion battery for the P-Sn @ G73 composite electrode material prepared in example 1 at different scan rates.
FIG. 12 is a graph showing the charge-discharge cycle curves of the pure tin phosphide electrode materials and the carbon content gradient P-Sn @ G material prepared in examples 1-5 and comparative example 1 as sodium ion battery half-cells at a rate of 0.1C.
FIG. 13 is a graph showing the rate of change of pure tin phosphide electrode materials and carbon content gradient P-Sn @ G materials prepared in examples 1-5 and comparative example 1 as half-cells of lithium ion batteries.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are provided to illustrate the present invention, but are not intended to limit the scope of the present invention.
The raw material components used in the invention can be obtained commercially, and the reagents used in the embodiment of the invention are all chemically pure. In the embodiment of the invention, the red phosphorus, the tin and the graphite exist in powder form (macroscopic), and the mesh number of the graphite is 3000.
Example 1
The embodiment provides a battery composite electrode material, and the preparation method comprises the following steps:
weighing 0.03 mol of red phosphorus simple substance, 0.04 mol of tin simple substance and 2.43G of graphite, assembling according to a ball-material ratio of 70:1, sealing in a stainless steel ball-milling tank under an argon atmosphere, taking out high-energy balls (the ball-milling media are stainless steel grinding balls with the diameter of 0.5 cm) at the rotating speed of 375 r/min for 30h, and obtaining the P-Sn @ G73 electrode material.
Example 2
The embodiment provides a battery composite electrode material, and the preparation method comprises the following steps:
weighing 0.03 mol of red phosphorus simple substance, 0.04 mol of tin simple substance and 5.69G of graphite, assembling according to a ball-material ratio of 80:1, sealing in a stainless steel ball-milling tank under an argon atmosphere, taking out high-energy balls (the ball-milling media are stainless steel grinding balls with the diameter of 0.5 cm) at the rotating speed of 400r/min for 30h, and obtaining the P-Sn @ G55 electrode material.
Example 3
The embodiment provides a battery composite electrode material, and the preparation method comprises the following steps:
weighing 0.03 mol of red phosphorus simple substance, 0.04 mol of tin simple substance and 1.42G of graphite, assembling according to a ball-material ratio of 80:1, sealing in a stainless steel ball-milling tank under an argon atmosphere, taking out high-energy balls (the ball-milling media are stainless steel grinding balls with the diameter of 0.5 cm) at the rotating speed of 375 r/min for 30h, and obtaining the P-Sn @ G82 electrode material.
Example 4
The embodiment provides a battery composite electrode material, and the preparation method comprises the following steps:
weighing 0.03 mol of red phosphorus simple substance, 0.04 mol of tin simple substance and 3.79G of graphite, assembling according to a ball-material ratio of 80:1, sealing in a stainless steel ball-milling tank under an argon atmosphere, taking out high-energy balls (the ball-milling media are stainless steel grinding balls with the diameter of 0.5 cm) at the rotating speed of 375 r/min for 30h, and obtaining the P-Sn @ G64 electrode material.
Example 5
The embodiment provides a battery composite electrode material, and the preparation method comprises the following steps:
weighing 0.03 mol of red phosphorus simple substance, 0.04 mol of tin simple substance and 0.63G of graphite, assembling according to a ball-material ratio of 80:1, sealing in a stainless steel ball-milling tank under an argon atmosphere, taking out high-energy balls (the ball-milling media are stainless steel grinding balls with the diameter of 0.5 cm) at the rotating speed of 375 r/min for 30h, and obtaining the P-Sn @ G64 electrode material.
Example 6
The embodiment provides a battery composite electrode material, and the preparation method comprises the following steps:
weighing 0.04 mol of red phosphorus simple substance, 0.04 mol of tin simple substance and 2.57G of graphite, assembling according to a ball-material ratio of 80:1, sealing in a stainless steel ball-milling tank under an argon atmosphere, taking out high-energy balls (the ball-milling medium is a stainless steel ball-milling ball with the diameter of 0.5 cm) at the rotating speed of 400r/min for 40h, and obtaining the P-Sn @ G73-2 electrode material.
Example 7
The embodiment provides a battery composite electrode material, and the preparation method comprises the following steps:
weighing 0.04 mol of red phosphorus simple substance, 0.04 mol of tin simple substance and 2.17G of graphite, assembling according to a ball-material ratio of 50:1, sealing in a stainless steel ball-milling tank under an argon atmosphere, taking out high-energy balls (the ball-milling medium is stainless steel balls with the diameter of 0.5 cm) at the rotating speed of 200r/min for 45h, and obtaining the P-Sn @ G73-3 electrode material.
Example 8
The embodiment provides a battery composite electrode material, and the preparation method comprises the following steps:
weighing 0.05mol of red phosphorus simple substance, 0.04 mol of tin simple substance and 2.70G of graphite, assembling according to a ball-material ratio of 80:1, sealing in a stainless steel ball-milling tank under an argon atmosphere, taking out high-energy balls (the ball-milling media are stainless steel grinding balls with the diameter of 0.5 cm) at the rotating speed of 700r/min for 15h, and obtaining the P-Sn @ G73-4 electrode material.
Example 9
The embodiment provides a battery composite electrode material, and the preparation method comprises the following steps:
weighing 0.008 mol of red phosphorus simple substance, 0.04 mol of tin simple substance and 2.15G of graphite, assembling according to a ball-material ratio of 20:1, sealing in a stainless steel ball-milling tank under an argon atmosphere, taking out high-energy balls (the ball-milling medium is a stainless steel ball-milling ball with the diameter of 0.5 cm) at the rotating speed of 100r/min for 50h, and obtaining the P-Sn @ G73-5 electrode material.
Example 10
The embodiment provides a battery composite electrode material, and the preparation method comprises the following steps:
weighing 0.2 mol of red phosphorus simple substance, 0.04 mol of tin simple substance and 4.70G of graphite, assembling according to a ball-material ratio of 150:1, sealing in a stainless steel ball-milling tank under an argon atmosphere, taking out high-energy balls (the ball-milling medium is a stainless steel ball-milling ball with the diameter of 0.5 cm) at the rotating speed of 900r/min for 5h, and obtaining the P-Sn @ G73-6 electrode material.
Comparative example 1
The comparative example provides a battery composite electrode material, and the preparation method comprises the following steps:
weighing 0.03 mol of red phosphorus simple substance and 0.04 mol of tin simple substance, assembling according to a ball-material ratio of 50:1, sealing in a stainless steel ball-milling tank under an argon atmosphere, taking out a high-energy ball (a ball-milling medium is a stainless steel ball with a diameter of 0.5 cm) at a rotation speed of 375 r/min for 30h, and obtaining the pure tin phosphide electrode material.
The performance of the composite electrode materials of examples 1 to 10 and comparative example 1 was tested, and the results were as follows:
as shown in fig. 1, as compared with a standard card, in the absence of graphite, a tin-phosphorus high-energy ball milling method obtains a tin phosphide phase with poor electrochemical performance, and with the increase of the graphite content, except for the addition of tin phosphide with poor crystalline phase in 10% graphite group, it can be noticed that the graphite peak of other groups is gradually increased, and the tin simple substance still maintains high crystallinity, which indicates that the addition of graphite prevents the tin and the phosphorus simple substance from undergoing a chemical reaction, and simultaneously ensures the monodispersity of red phosphorus, tin and graphite.
As shown in fig. 2, the graphite used in the embodiment of the present invention is flake graphite, which can ensure the structural stability during high-energy ball milling.
As shown in fig. 3, the raw material red phosphorus in the examples of the present invention had a large particle size before ball milling.
As shown in FIG. 4, the distinct difference between the prepared tin phosphide electrode material and the red phosphorus phase proves that the combination reaction does occur, but the larger agglomeration phenomenon still exists, the dispersibility is poor, and the poor conductivity is indirectly caused.
As shown in fig. 5, in an SEM image of the phosphorus-tin @ graphite composite electrode material P-Sn @ G73 obtained in example 1, it can be seen that in the micro-nano structure, phosphorus, tin, and graphite each exhibit their own monodispersity, and the graphite maintains the structure before ball milling, while the particle size of red phosphorus is reduced, and the synergistic effect of the three improves the conductivity of the material to enhance its electrochemical energy storage performance.
As shown in FIG. 6, the P-Sn @ G73 composite electrode material prepared in example 1 contains P, Sn and C elements in proportion.
As shown in FIG. 7, in the P-Sn @ G73 composite electrode material prepared in example 1, graphite, red phosphorus and tin are tightly combined together to form a chemical bond, which is favorable for electron transport.
As shown in FIG. 8, the P-Sn @ G73 composite electrode material prepared in example 1 was measured at scan rates of 0.2 mV/s, 0.5 mV/s, 1 mV/s, 2 mV/s, and 5 mV/s. The lithium storage potential of the material is reflected at the peaks of different voltages, which shows that the material has good electrochemical performance when being used as a lithium ion battery cathode material.
As shown in FIG. 9, the specific capacities of the P-Sn @ G materials of examples 1-5 as the negative electrode of the lithium ion battery after 250 cycles were 1061mAh/G (P-Sn @ G73), 830mAh/G (P-Sn @ G64), 645mAh/G (P-Sn @ G82), and 555mAh/G (P-Sn @ G55), respectively, and the P-Sn @91 composite electrode material containing 10% pure tin phosphide and graphite was earlier less than 200 mAh/G. The inhibition of phosphorus-tin two-phase reaction of the graphite is proved, the electrochemical performance is greatly improved, and meanwhile, the optimal specific capacity can be obtained by proper graphite addition, and the cycle performance is good.
As shown in fig. 10, P-Sn @ G73 of example 1 is the best of the rate capability of all materials, with current densities of 0.2C, 0.4C, 0.5C, 1C, 1.5C, 2C, 4C, 8C, and finally back to 0.2C corresponding to specific capacities of 720mAh/G, 623mAh/G, 556mAh/G, 508mAh/G, 487mAh/G, 453mAh/G, 411mAh/G, 375mAh/G, 553mAh/G, indicating that it retains good electrochemical performance at high current densities.
As shown in FIG. 11, it can be seen that at the scan rates 0.2 mV/s, 0.5 mV/s, 1 mV/s, 2 mV/s, 5 mV/s. The sodium storage potential of the material is reflected at the peaks of different voltages, which shows that the material has good electrochemical performance as a negative electrode material of a sodium-ion battery.
As shown in FIG. 12, the specific capacities of the prepared materials as the negative electrode of the sodium ion battery after 100 cycles of cycling are 143mAh/G (P-Sn @ G73), 124mAh/G (P-Sn @ G64), 98mAh/G (P-Sn @ G82), 42mAh/G (P-Sn @ G55) and 40mAh/G (P-Sn @ G95), respectively, and pure tin phosphide has almost no sodium storage capacity. Meanwhile, the specific capacities of P-Sn @ G73-2, P-Sn @ G73-3, P-Sn @ G73-4, P-Sn @ G73-5 and P-Sn @ G73-6 are respectively 140mAh/G, 125mAh/G, 110mAh/G, 53mAh/G and 45mAh/G after 100 cycles of circulation. The results prove that the graphite can prevent phosphorus-tin two-phase reaction, the electrochemical performance is greatly improved, and simultaneously, the proper graphite addition can obtain the optimal specific capacity and the cycle performance is good.
As shown in fig. 13, P-Sn @ G73 is the best of the rate capability of all materials, with current densities of 0.1C, 0.2C, 0.4C, 0.5C, 1C, 1.5C, 2C, 4C, and finally back to 0.2C corresponding to specific capacities of 228mAh/G, 195mAh/G, 171 mAh/G, 156mAh/G, 136mAh/G, 121mAh/G, 113mAh/G, 98mAh/G, 201mAh/G, indicating that it can maintain good electrochemical performance at high current densities.
Finally, the method of the present invention is only a preferred embodiment and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (2)

1. The preparation method of the battery composite electrode material is characterized by comprising the following steps of:
mixing a phosphorus simple substance, a tin simple substance and graphite, and performing ball milling under an inert gas atmosphere to obtain the compound;
the molar ratio of the phosphorus simple substance to the tin simple substance is 1: 5-5: 1;
the adding amount of the graphite is 1: 1-1: 9 of the total mass of the phosphorus simple substance and the tin simple substance;
the diameter of the ball milling medium for ball milling is 0.1-0.5 cm;
the ball-material ratio of the ball milling is 20: 1-150: 1;
the rotation speed of the ball mill is 300 r/min-400 r/min, and the time is 30-40 h;
the battery composite electrode material is a phosphorus-tin @ graphite composite electrode material, the material has a micro-nano structure that each component has monodispersity and is mutually connected, a certain nano pore is formed on the surface of phosphorus and tin, and graphite is tightly combined on the surface of phosphorus and tin as an intercalation.
2. The preparation method according to claim 1, wherein the molar ratio of the elemental phosphorus to the elemental tin is (1-5): 4.
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