CN108598475B - Phosphorus, sulfur and selenium series anode materials with adjustable composition and structure for ion batteries - Google Patents

Phosphorus, sulfur and selenium series anode materials with adjustable composition and structure for ion batteries Download PDF

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CN108598475B
CN108598475B CN201810379025.5A CN201810379025A CN108598475B CN 108598475 B CN108598475 B CN 108598475B CN 201810379025 A CN201810379025 A CN 201810379025A CN 108598475 B CN108598475 B CN 108598475B
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ion battery
electrode material
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sulfur
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余家乐
张海燕
李文武
张宇杰
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Guangdong University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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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
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    • 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
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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    • H01M4/5815—Sulfides
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Abstract

本发明属于离子电池材料领域，尤其涉及离子电池用成分结构可调控的磷硫硒系列负极材料。本发明提供了一种离子电池负极材料，为：非晶态P4SxSe3‑x；其中，x为0或1或2或3。本发明还提供了一种上述离子电池负极材料的制备方法，本发明还提供了一种上述离子电池负极材料或上述制备方法得到的产品在锂离子电池和/或钠离子电池领域的应用。经试验测定可得，本发明提供的技术方案制得的产品，具有容量高、倍率性能好、循环性能好的优点；产品无定形非晶态产品结构，短程有序的结构恢复更加容易，有利于电极材料在充放电过程中保持稳定；解决了现有技术中，离子电池的负极材料存在着容量低、倍率性能差以及循环稳定性差的技术缺陷。

Figure 201810379025

The invention belongs to the field of ion battery materials, in particular to a phosphorus-sulfur-selenium series negative electrode material whose composition and structure can be adjusted for ion batteries. The invention provides an ion battery negative electrode material, which is: amorphous P 4 S x Se 3-x ; wherein, x is 0 or 1 or 2 or 3. The present invention also provides a preparation method of the above-mentioned ion battery negative electrode material, and the present invention also provides the application of the above-mentioned ion battery negative electrode material or the product obtained by the above-mentioned preparation method in the field of lithium ion batteries and/or sodium ion batteries. It can be obtained through experiments that the product prepared by the technical solution provided by the present invention has the advantages of high capacity, good rate performance and good cycle performance; the product has an amorphous amorphous product structure, and the short-range ordered structure recovery is easier, and there are It is beneficial to keep the electrode material stable during the charging and discharging process; it solves the technical defects of low capacity, poor rate performance and poor cycle stability of the negative electrode material of the ion battery in the prior art.

Figure 201810379025

Description

Phosphorus-sulfur-selenium series cathode material with adjustable component structure for ion battery
Technical Field
The invention belongs to the field of ion battery materials, and particularly relates to a phosphorus-sulfur-selenium series negative electrode material with an adjustable component structure for an ion battery.
Background
The increasingly depleted non-renewable energy and the constantly deteriorating natural environment have stimulated the pursuit of new renewable energy by mankind. Therefore, human beings continuously develop new renewable energy sources such as wind energy, solar energy, tidal energy and the like, and store the renewable energy sources by using a static energy storage power station so as to improve the energy utilization efficiency. Meanwhile, electric vehicles and portable electronic devices gradually come into the lives of people. Currently, in the field of energy storage, lithium ion batteries have been used in the fields of mobile energy storage such as 3C electronic products and electric vehicles due to their advantages of environmental protection, high energy density, high operating voltage, and the like; the energy density of the sodium ion battery is lower than that of the lithium ion battery, but the sodium ion battery benefits from the abundant sodium resource of the earth and has relatively low economic cost, so that the sodium ion battery can be used in the static energy storage fields of UPS power supplies, communication base station power supplies, pumped storage power stations, industrial heat storage systems and the like.
At present, most of commercial lithium ion batteries adopt graphite as a negative electrode material, but the theoretical capacity of the lithium ion batteries is only 372mAh g-1And can not meet the current market demand. In addition, graphite has problems of poor rate capability, lithium dendrite, and the like. At present, carbon-based materials, silicon-based materials and tin-based materials, which are much attention paid by researchers, cannot meet the current needs due to the problems of poor cycle stability caused by small specific capacity and volume expansion. In addition, a very important indicator for battery applications is cycling performance. The crystal material has a regular crystal structure, so that the structure is easy to collapse after multiple charge and discharge cycles, and the cycle performance is poor.
Therefore, the development of phosphorus-sulfur-selenium series negative electrode materials with adjustable component structures for ion batteries is used for solving the technical defects of low capacity, poor rate capability and poor cycle stability of the negative electrode materials of the ion batteries in the prior art, and the problem to be solved by the technical staff in the field is urgently needed.
Disclosure of Invention
In view of the above, the invention provides a phosphorus-sulfur-selenium series negative electrode material with an adjustable component structure for an ion battery, which is used for solving the technical defects of low capacity, poor rate capability and poor cycle stability of the negative electrode material of the ion battery in the prior art.
The invention provides an ion battery cathode material, which comprises the following components in parts by weight: amorphous state of P4SxSe3-x(ii) a Wherein x is 0 or 1 or 2 or 3.
The invention also provides a preparation method of the ion battery cathode material, which comprises the following steps: mixing phosphorus powder, sulfur powder and selenium powder, and ball-milling to obtain a product;
wherein, the ball milling process is carried out under the protection of inert gas.
Preferably, the feeding ratio of the phosphorus powder, the sulfur powder and the selenium powder is (3.9-4.1): (0-3): 0-3) in terms of molar parts.
Preferably, the ball mass ratio of the ball milling is (20-25): 1.
Preferably, the rotation speed of the ball milling is 1100-1200 r/min, and the ball milling time is 5-10 h.
Preferably, the inert gas is nitrogen and/or argon.
Preferably, the ball milling tank and the ball milling beads of the ball mill are made of the same material.
Preferably, the material of the ball milling tank is stainless steel or hard alloy.
The invention also provides an application of the negative electrode material of the ion battery or the product obtained by the preparation method in the field of lithium ion batteries and/or sodium ion batteries.
In summary, the present invention provides an ion battery anode material, which is: amorphous state of P4SxSe3-x(ii) a Wherein x is 0 or 1 or 2 or 3. The invention also provides a preparation method of the ion battery cathode material, which comprises the following steps: mixing phosphorus powder, sulfur powder and selenium powder, and ball-milling to obtain a product; wherein, the ball milling process is carried out under the protection of inert gas. The invention also provides an application of the negative electrode material of the ion battery or the product obtained by the preparation method in the field of lithium ion batteries and/or sodium ion batteries. The product prepared by the technical scheme provided by the invention has the advantages of high capacity, good rate capability and good cycle performance; the amorphous product structure of the product is easier to recover from the short-range ordered structure, and is beneficial to keeping the stability of the electrode material in the charging and discharging processes. The phosphorus-sulfur-selenium series cathode material with the adjustable component structure for the ion battery solves the problem that the cathode material of the ion battery has low capacity in the prior artPoor rate capability and poor cycle stability.
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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 embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is P4SSe2X-ray diffraction pattern of elemental substance P, S, Se;
FIG. 2 is P4Se3X-ray diffraction pattern of
FIG. 3 is P4SSe2A spectrum of (a);
FIG. 4 is P4SSe2Taking the curve as a charge-discharge curve of a negative electrode material of the lithium ion battery;
FIG. 5 is P4SSe2The material is used as a charge-discharge curve of a negative electrode material of a sodium ion battery.
Detailed Description
The embodiment of the invention provides a phosphorus-sulfur-selenium series cathode material with an adjustable component structure for an ion battery, which is used for solving the technical defects of low capacity, poor rate capability and poor cycle stability of the cathode material of the ion battery in the prior art.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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 order to explain the present invention in more detail, the following describes the phosphorus-sulfur-selenium series anode material with adjustable composition structure for ion batteries specifically with reference to the examples.
Example 1
This example is to prepare amorphous P4S3In the following description.
2.8147g of phosphorus powder with the purity of 99.9 percent and 2.1853g of sulfur powder with the purity of 99.9 percent are respectively weighed and mixed, and are ball-milled for 10 hours in a ball-milling tank under the protection of nitrogen and the conditions that the ball mass ratio is 25:1 and the rotating speed is 1200r/min to obtain P4S3(ii) a Wherein, the ball milling pot and the ball milling beads are made of stainless steel.
And (3) obtaining a prepared sample with an atomic ratio of P: S-4: 3 and an amorphous substance by X-ray diffraction analysis and element quantitative analysis.
Example 2
This example is to prepare amorphous P4Se3In the following description.
1.7171g of phosphorus powder with the purity of 99.9 percent and 3.2829g of selenium powder with the purity of 99.9 percent are respectively weighed and mixed, and are ball-milled for 10 hours in a ball-milling tank under the protection of argon gas and the conditions that the ball mass ratio is 25:1 and the rotating speed is 1200r/min to obtain P4Se3(ii) a Wherein, the ball milling pot and the ball milling beads are made of hard alloy.
And (3) obtaining a prepared sample with an atomic ratio of P to Se of 4 to 3 and an amorphous substance by X-ray diffraction analysis and element quantitative analysis.
Example 3
This example is to prepare amorphous P4SSe2In the following description.
1.9736g of phosphorus powder with the purity of 99.9 percent, 0.5108g of sulfur powder with the purity of 99.9 percent and 2.5156g of selenium powder with the purity of 99.9 percent are respectively weighed and mixed, and are ball-milled for 10 hours in a ball-milling tank under the protection of mixed gas of nitrogen and argon, the ball mass ratio is 25:1 and the rotating speed is 1100r/min, so that P is obtained4SSe2(ii) a Wherein, the ball milling pot and the ball milling beads are made of stainless steel.
By X-ray diffraction analysis and element quantitative analysis, the prepared sample has the atomic ratio of P to S to Se of 4 to 1 to 2, and is an amorphous substance.
Example 4
This example is to prepare amorphous P4S2Specific examples of Se.
2.3212g of phosphorus powder with the purity of 99.9 percent, 1.2014g of sulfur powder with the purity of 99.9 percent and 1.4795g of selenium powder with the purity of 99.9 percent are respectively weighed and mixed, and are ball-milled for 10 hours in a ball-milling tank under the protection of mixed gas of nitrogen and argon, the ball mass ratio is 25:1 and the rotating speed is 1200r/min, so that P is obtained4S2Se; wherein, the ball milling pot and the ball milling beads are made of stainless steel.
By X-ray diffraction analysis and element quantitative analysis, the prepared sample has the atomic ratio of P to S to Se of 4 to 2 to 1, and is an amorphous substance.
Example 5
This example is a specific example of measuring the X-ray diffraction pattern of the products obtained in examples 1 to 4.
The measurement results are shown in FIG. 1 and FIG. 2, where P is shown in FIG. 14SSe2Comparison with the X-ray diffraction of the simple substance P, S, Se, P in FIG. 24Se3X-ray diffraction pattern of (a).
As can be seen from FIG. 1, P is4SSe2The X-ray diffraction results of (A) are different from those of P, S, Se elementary substance. And, P4SSe2Diffraction peak of (2) and standard PDF card (P)4SSe2: PDF #44-1062), P4Se3Diffraction peak of (2) and standard PDF card (P)4Se3: PDF #27-0361), indicating successful sample preparation.
In addition, P4Se3And P4SSe2The diffraction peak signal is very weak, only two weak 'steamed bread peaks' exist, and the P prepared by the high-energy ball milling method is preliminarily shown4Se3And P4SSe2The diffraction peak of the phosphorus-sulfur-selenium compound is an amorphous compound.
P4S2Se and P4S3The measurement results are similar to the above results and are not described in detail herein.
Example 6
This example is an energy spectrum of the product obtained in examples 1 to 4.
The results of the measurements are shown in FIG. 3, where P is shown in FIG. 34SSe2Energy spectrum of (2).
As can be seen from fig. 3, the compound consists of P, S, Se three elements, and the atomic ratio is P: S: Se ═ 3.951:1:1.993, very close to 4:1:2, with small amounts of foreign elements such as copper, carbon coming from the test copper mesh and the contaminating carbon source, respectively. Thus illustrating the method for preparing P4SSe2Phosphorus sulfur selenium compounds are feasible.
And (4) measuring energy spectrums of the other three compounds, wherein the atomic ratio of each product is the same as that of the target compound, and the details are not repeated.
Example 7
This example is a specific example of observing the structure of the product prepared in examples 1 to 4 using a scanning electron microscope.
The microscopic appearance of the prepared product is nano particles, and the smaller primary particle clusters are excessively agglomerated to form larger secondary particles, so that the transmission and permeation of electrolyte are facilitated, and most importantly, the tap density of an electrode is improved, and finally, the energy density of the whole battery is improved.
Example 8
The present embodiment is a specific embodiment of observing the structure of the product prepared in embodiments 1 to 4 by using a transmission electron microscope, and performing corresponding detection on the electron diffraction pattern thereof.
The prepared products are all in typical amorphous structures as can be seen from the field of view of the microscope; the amorphous structure material can reserve a large amount of buffer space for volume expansion in the charging and discharging process, so that the electrode material is not easy to pulverize and fall off. More importantly, the short-range ordered structure makes the structure recovery relatively easy, thereby being beneficial to keeping the electrode material stable in the charging and discharging process.
Example 9
This example is a specific example of the constant current charge-discharge test curves of lithium ion batteries and sodium ion batteries using the products prepared in examples 1 to 4 as the negative electrodes, respectively.
Wherein, FIG. 4 shows the case of P4SSe2FIG. 5 shows the charge/discharge curve of a negative electrode lithium ion battery using P4SSe2As negative electrode sodium ionThe charge and discharge curve of the battery.
In a lithium ion battery, P4SSe2The lithium storage capacity is up to 1456mAh/g, which is close to the theoretical lithium storage capacity (1537mAh/g), and the first coulombic efficiency is up to 86%. In sodium ion batteries, P4SSe2The sodium storage capacity is up to 813mAh/g, and the first coulombic efficiency is up to 80%.
The above assay was repeated for the remaining three compounds, all of which gave similar experimental results, and will not be described further herein.
In the invention, the research focus is changed to the research of phosphorus and VIA composite materials (sulfur and selenium) and aims to synthesize amorphous P4SxSe3-x(X is more than or equal to 0 and less than or equal to 3) negative electrode material. Selenium (Se) has good conductivity (approximatively 10-5S cm-1) and high theoretical specific capacity (678mA h g-1); meanwhile, the presence of P — Se bonds can inhibit the dissolution of Se and its reaction intermediates in the electrolyte.
Further, the sulfur-rich phosphorus sulfur compound has lithium and sodium storage properties different from those of sulfur, which has higher conductivity, thereby exhibiting excellent lithium storage capacity. At the same time, due to the existence of P-S bond, P is enabled4SxSe3-x(X is more than or equal to 0 and less than or equal to 3) has higher cycle stability. In addition, a large amount of buffer space can be reserved for volume expansion in the charge-discharge process of the amorphous structure material, so that the electrode material is not easy to pulverize and fall off. More importantly, the short-range ordered structure makes the structure recovery relatively easy, thereby being beneficial to keeping the electrode material stable in the charging and discharging process.
In the technical scheme provided by the invention, P, S, Se is compounded at the same time to prepare the amorphous P-S-Se material. Because the three elements are all high-capacity elements, the three elements are used in the same system to be beneficial to generating P with high capacity and high cycling stability4SxSe3-x(X is more than or equal to 0 and less than or equal to 3) electrode material.
S, Se the intermediate products of the reaction process are readily soluble in the electrolyte, leading to rapid capacity fade and reduced cell cycling stability. Therefore, in the invention, P-S bond and P-Se bond are introduced, thereby reducing the shuttle effect of S and Se through chemical recombination. Document retrieval systemAt present, there is no P4SxSe3-x(X is more than or equal to 0 and less than or equal to 3) in the aspect of electrochemical work.
The preliminary research shows that the system is used as the lithium ion battery cathode material, and the specific capacity is 1500--1In between, the first coulombic efficiency is about 80%.
Meanwhile, EIS test and CV test show that the material has better reaction kinetics, and Li+And Na+The transmission speed is faster, which corresponds to its superior rate capability. The above results show that P4SxSe3-x(0. ltoreq. X. ltoreq.3) is an excellent electrode material.
According to the technical scheme, the phosphorus-sulfur-selenium series cathode material with the adjustable component structure for the ion battery has the following advantages:
(1) the invention provides a method for preparing P4SxSe3-x(X is more than or equal to 0 and less than or equal to 3) the method of the cathode material is beneficial to improving the production efficiency. The high-energy ball milling method can be adopted to prepare the P in large batch and large scale4SxSe3-x(X is more than or equal to 0 and less than or equal to 3) negative electrode material. Compared with the traditional chemical synthesis, the production process can be monitored by a machine program without complex manual operation and complex calculation, so that the production efficiency can be greatly improved. In addition, the high-energy ball milling method can easily prepare amorphous P4SxSe3-x(X is more than or equal to 0 and less than or equal to 3), and has great technical progress compared with the defects of complex preparation method, high cost and low yield of the traditional amorphous material.
(2) P prepared by the invention4SxSe3-x(X is more than or equal to 0 and less than or equal to 3) the cathode material is used for the cathode of the lithium ion battery and the sodium ion battery, which is beneficial to improving the cycle performance of the battery. At present, most of negative electrode materials of lithium ion batteries and sodium ion batteries are crystal materials, and the crystal materials have regular crystal structures, so that the structures are easily collapsed after multiple charge and discharge cycles, and the cycle performance is poor. P prepared by the invention4SxSe3-x(X is more than or equal to 0 and less than or equal to 3) the negative electrode material is in an amorphous structure, and the amorphous material has an amorphous structureThe structure, so there is no problem of structural damage. In addition, a large amount of buffer space can be reserved for volume expansion in the charging and discharging process of the amorphous material, so that the electrode material is not easy to pulverize and fall off. More importantly, the short-range order structure makes the structure recovery relatively easy. Therefore, the lithium ion battery and the sodium ion battery can have good cycle stability when applied to the lithium ion battery and the sodium ion battery.
(3) P prepared by the invention4SxSe3-x(X is more than or equal to 0 and less than or equal to 3) the negative electrode material is used for the negative electrode of the lithium ion battery and the sodium ion battery and is beneficial to improving the specific capacity of the battery. Since P, S, Se elements have large theoretical capacity, the material prepared by highly compounding two or three elements also has large capacity, such as P4SSe2The theoretical lithium storage capacity of the graphite material is as high as 1537mAh/g, which is far higher than that of the conventional graphite material (372 mAh/g).
(4) P prepared by the invention4SxSe3-x(X is more than or equal to 0 and less than or equal to 3) the cathode material is used for the cathode of the lithium ion battery and the sodium ion battery, and is beneficial to improving the first coulombic efficiency and the rate capability of the battery. In the traditional lithium-sulfur battery, sodium-sulfur battery, lithium-selenium battery and sodium-selenium battery, because sulfur and selenium elements have shuttle effect, an intermediate product in the electrode reaction process can be dissolved in electrolyte, so that the first coulombic efficiency and rate capability are reduced. However, in the present invention, P4SxSe3-x(X is more than or equal to 0 and less than or equal to 3) in the cathode material system, due to the P-S bond and the P-Se bond formed in the high-energy ball milling process, the strong interaction of the chemical bonds ensures that S, Se and reaction intermediate products thereof are not dissolved in the electrolyte, thereby greatly improving the first coulombic efficiency and rate capability of the battery.
(5) P prepared by the invention4SxSe3-x(X is more than or equal to 0 and less than or equal to 3) the cathode material is used for the cathode of the lithium ion battery and the sodium ion battery, which is beneficial to improving the reaction kinetics of the battery. The P-S bond and the P-Se bond formed in the high-energy ball milling process enable the microstructure of the electrode material to be kept stable, S, Se and reaction intermediate products thereof are not dissolved in the electrolyte, so that the electrolyte always keeps higher ionic conductivity, and the impedance of the battery is not reduced. In addition, electrolytic reactionIn the process, a fast ion conductor is generated, so that the ionic conduction of the battery is greatly improved, the electrochemical polarization of the material is reduced, and the reaction kinetics of the material is improved.
In summary, the present invention provides an ion battery anode material, which is: amorphous state of P4SxSe3-x(ii) a Wherein x is 0 or 1 or 2 or 3. The invention also provides a preparation method of the ion battery cathode material, which comprises the following steps: mixing phosphorus powder, sulfur powder and selenium powder, and ball-milling to obtain a product; wherein, the ball milling process is carried out under the protection of inert gas. The invention also provides an application of the negative electrode material of the ion battery or the product obtained by the preparation method in the field of lithium ion batteries and/or sodium ion batteries. The product prepared by the technical scheme provided by the invention has the advantages of high capacity, good rate capability and good cycle performance; the amorphous product structure of the product is easier to recover from the short-range ordered structure, and is beneficial to keeping the stability of the electrode material in the charging and discharging processes. The phosphorus-sulfur-selenium series cathode material with the adjustable component structure for the ion battery provided by the invention solves the technical defects of low capacity, poor rate capability and poor cycle stability of the cathode material of the ion battery in the prior art.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (6)

1. The negative electrode material of the ion battery is characterized by comprising the following components in parts by weight: amorphous state of P4SxSe3-x(ii) a Wherein x is 1 or 2;
the preparation method of the negative electrode material of the ion battery comprises the following steps: mixing phosphorus powder, sulfur powder and selenium powder, and ball-milling to obtain a product;
wherein, the ball milling process is carried out under the protection of inert gas;
the ball mass ratio of the ball milling is (20-25) to 1;
the rotating speed of the ball milling is 1100-1200 r/min, and the ball milling time is 5-10 h.
2. The negative electrode material for ion batteries of claim 1, wherein the ratio of phosphorus powder, sulfur powder and selenium powder is (3.9-4.1): (0-3): 0-3).
3. The ion battery anode material according to claim 1, wherein the inert gas is nitrogen and/or argon.
4. The negative electrode material for the ion battery as claimed in claim 1, wherein the ball milling pot and the ball milling beads are made of the same material.
5. The negative electrode material for the ion battery as claimed in claim 4, wherein the material of the ball milling pot is stainless steel or hard alloy.
6. The application of the negative electrode material of the ion battery as claimed in any one of claims 1 to 5 in the field of lithium ion batteries and/or sodium ion batteries.
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