CN114784279A - Preparation method of silicon-based negative electrode material of lithium ion battery - Google Patents
Preparation method of silicon-based negative electrode material of lithium ion battery Download PDFInfo
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- CN114784279A CN114784279A CN202210442508.1A CN202210442508A CN114784279A CN 114784279 A CN114784279 A CN 114784279A CN 202210442508 A CN202210442508 A CN 202210442508A CN 114784279 A CN114784279 A CN 114784279A
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- 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
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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
- H01M4/386—Silicon or alloys based on silicon
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
Abstract
The invention belongs to the technical field of preparation of lithium ion battery electrode materials, and particularly relates to a preparation method of a silicon-based negative electrode material of a lithium ion battery, which comprises the following steps: 1) respectively weighing silicon powder and metal hydride powder, putting the silicon powder and the metal hydride powder into a ball milling tank, and 2) putting the ball milling tank on a planetary ball mill for ball milling, and uniformly mixing; 3) putting the ball-milled dry powder into a die, and tabletting the powder on a powder tabletting machine; 4) and (3) putting the pressed sheet into a tubular furnace filled with argon for calcination, and cooling to room temperature after the calcination is finished to obtain the required silicon-based negative electrode material of the lithium ion battery. According to the invention, metal hydride and silicon are compounded to be used as the negative electrode material of the lithium ion battery, the hydride and silicon powder are combined to reduce oxygen on the surface of the silicon, the formed metal oxide can inhibit the volume expansion of the silicon, and meanwhile, lithium at a high temperature can bond metal and silicon, so that the cycle performance is more stable, and the conductivity of the silicon is improved.
Description
Technical Field
The invention belongs to the technical field of preparation of lithium ion battery electrode materials, and particularly relates to a preparation method of a silicon-based negative electrode material of a lithium ion battery.
Background
At present, lithium ion batteries have the characteristics of high energy density, long cycle life, environmental friendliness and the like, and are widely applied to the fields of electric automobiles, portable electronic products and the like. However, the current commercialized graphite cathode can not meet the demand of the lithium ion battery due to low theoretical capacity (372 mAh/g). In this case, silicon has ultra-high specific capacity (4200 mAh/g), low working potential (0.4 VvsLi/Li)+) And abundant natural reserve capacity, and the like, and is widely concerned by people. However, silicon undergoes a sharp volume expansion (-300%) during the lithium extraction/insertion process, resulting in pulverization of the electrode material and a decrease in conductivity, resulting in rapid decay of the silicon capacity and a decrease in cycle life. Therefore, in order to better improve the performance of the lithium ion battery and meet the requirements of the lithium ion battery, the research and development of the silicon cathode with high performance, high specific capacity and high structural stability are very important.
The metal hydride negative electrode is an option applied in the field of high-performance lithium ion batteries, and at present, related documents mention the application of metal hydrides in lithium ion batteries. For example, chinese patent publication No. CN110518195A discloses a method for uniformly grinding a nano silicon/graphene composite material and a metal hydride as a negative electrode material of a lithium ion battery. Chinese patent publication No. CN108767198B discloses a method for preparing a titanium-based metal hydride negative electrode of a lithium ion battery, in which a target material is prepared by mixing titanium-based metal hydride and a carbonaceous material, and a thin film pole piece is prepared by magnetron sputtering, which indicates that the metal hydride has great potential for improving the performance of the lithium ion battery.
However, the lithium ion battery silicon base material prepared by using metal hydride in the existing method has the problems of weak lithium conducting capability and unstable cycle performance of silicon. Therefore, it is necessary to optimize and improve it.
Disclosure of Invention
The present invention has been made to overcome the above problems occurring in the conventional art, and an object of the present invention is to provide a method for manufacturing a display deviceThe preparation method of the silicon-based negative electrode material of the lithium ion battery comprises the steps of introducing metal hydride modified nano-silicon as the negative electrode material, mixing the metal hydride modified nano-silicon with silicon powder through ball milling to generate an interface reaction, and then sintering at high temperature to dehydrogenate the hydride and reduce oxygen-containing groups SiO on the surface of the siliconxConversion to MOxAnd the metal and the silicon can form a metal silicide MSixAs a buffer phase, the lithium-conducting capacity of the silicon is improved, and the cycle performance of the silicon is more stable.
In order to achieve the technical purpose and achieve the technical effect, the invention is realized by the following technical scheme:
a preparation method of a silicon-based negative electrode material of a lithium ion battery comprises the following steps:
1) according to the mass ratio of 8-40: 1, respectively weighing silicon powder and metal hydride powder, and putting the silicon powder and the metal hydride powder into a ball milling tank, wherein the ball-to-material ratio is 20-40: 1;
2) placing the ball milling tank on a planetary ball mill for ball milling to uniformly mix the silicon powder and the metal hydride powder;
3) putting the ball-milled dry powder into a die, and tabletting the powder on a powder tabletting machine;
4) and (3) putting the pressed sheet into a tubular furnace filled with argon, heating to 600-900 ℃, calcining for 4-8 h at the temperature, and cooling to room temperature after calcining to obtain the required silicon-based negative electrode material of the lithium ion battery.
Further, in the preparation method of the silicon-based negative electrode material of the lithium ion battery, in the step 1), the silicon powder is nano silicon powder which is obtained by alcohol water milling.
Further, in the preparation method of the silicon-based negative electrode material of the lithium ion battery, in step 1), the metal hydride powder includes at least one of titanium hydride, magnesium hydride and lithium hydride powder.
Further, in the preparation method of the silicon-based negative electrode material of the lithium ion battery, in the step 1), the weighing and ball milling processes are performed in a glove box filled with argon.
Further, in the preparation method of the silicon-based negative electrode material of the lithium ion battery, in the step 2), the planetary ball mill performs ball milling for 6 hours at the speed of 300-500 r/min.
Further, in the preparation method of the silicon-based negative electrode material of the lithium ion battery, in the step 3), the gauge pressure of the powder tablet press is controlled at 12MPa, and the compression time is 5 min.
Further, according to the preparation method of the silicon-based negative electrode material of the lithium ion battery, in the step 4), the temperature rise rate of the tubular furnace is 2 ℃/min, and the cooling rate after calcination is-2 ℃/min.
Further, in the preparation method of the silicon-based negative electrode material of the lithium ion battery, in the step 4), the temperature is increased to 800 ℃ and then the material is calcined for 6 hours.
The beneficial effects of the invention are:
1. the preparation method provided by the invention has scientific and reasonable design, and the titanium hydride material is compounded with silicon for the first time, so that the possibility of compounding the metal hydride and the silicon is provided. The synthesis process mainly comprises ball milling and calcining, has no complex process flow, and is simple in preparation process and environment-friendly.
2. In the process of the Si/MHx composite material prepared by the ball milling method and the simple heat treatment process, because metal atoms generated by dehydrogenation of metal hydride during high-temperature calcination have strong reducibility, the Si/MHx composite material can be used for preparing SiO on the surface of the nano siliconxReduction to MOxAnd further, the bonding force between silicon and an SEI layer (solid electrolyte interface layer) is improved, the volume expansion of silicon is relieved, the problem of SEI layer shedding is inhibited, and the chemical stability of silicon is improved.
Of course, it is not necessary for any product to achieve all of the above advantages at the same time in the practice of the invention.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the description below are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a graph showing the cycle life of a half-cell in examples 1 to 4 of the present invention, in which nano silicon powder and titanium hydride powder are compounded in different proportions;
FIG. 2 is a graph showing the charge and discharge curves of the half-cell after the nano silicon powder and the titanium hydride powder are compounded in different proportions in examples 1 to 4 of the present invention;
FIG. 3 is an impedance diagram of a half-cell in examples 1 to 4 of the present invention, in which nano silicon powder and titanium hydride powder are compounded at different ratios;
FIG. 4 is a scanning electron microscope image of the silica nanoparticles used in examples 1 to 4 of the present invention.
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.
The specific embodiment of the invention is as follows:
example 1
A preparation method of a silicon-based negative electrode material of a lithium ion battery specifically comprises the following steps:
1) 1.8g of nano silicon powder and 0.2g of titanium hydride powder are respectively weighed in a glove box filled with argon, and put into a ball milling tank, and 60g of zirconia balls are added into the ball milling tank, wherein the ball-to-material ratio is 30: 1.
2) Placing the ball milling tank on a planetary ball mill, carrying out ball milling for 6h at the rotating speed of 400r/min, and uniformly mixing the nano silicon powder and the titanium hydride powder;
3) putting the ball-milled dry powder into a die, and tabletting the powder on a powder tabletting machine under the pressure of 12MPa for 5 min;
4) and (3) putting the product obtained in the step 3) into a tubular furnace filled with argon, calcining for 6 hours at 800 ℃ at the heating rate of 2 ℃/min, and marking the calcined product as the required composite material as Si @0.1TiH 2.
Example 2
In example 1On the basis of keeping other conditions unchanged, the mass of the nano silicon powder in the step 1) is adjusted to be 1.84g, the mass of the titanium hydride powder is adjusted to be 0.16g, and the obtained product is marked as Si @0.08TiH2。
Example 3
On the basis of example 1, other conditions are kept unchanged, the mass of the nano silicon powder in the step (1) is adjusted to be 1.9g, the mass of the titanium hydride powder is adjusted to be 0.1g, and the obtained product is marked as Si @0.05TiH2。
Example 4
On the basis of example 1, the mass of the nano silicon powder in the step (1) is adjusted to be 1.94g and the mass of the titanium hydride powder is adjusted to be 0.06g while keeping other conditions unchanged, and the obtained product is recorded as Si @0.03TiH2。
Fig. 1 shows a cycle life diagram of a half-cell in which nano silicon powder and titanium hydride powder are compounded in different proportions, and it can be seen from the diagram that cycle life performance of the nano silicon powder and titanium hydride powder after alcohol water milling is obviously improved compared with pure silicon. The electrochemical performances of the two groups of Si @0.08TiH2 and Si @0.05TiH2 are more stable, and the introduction of titanium hydride can improve the electrochemical stability of silicon.
It can be seen from fig. 2 that the introduction of titanium hydride can not only improve the electrochemical stability of silicon, but also improve the coulombic efficiency of the first turn of silicon. The first-turn coulombic efficiency of the original silicon is 86.4%, and after the original silicon is subjected to alcohol water milling and 5% of titanium hydride is added, the first-turn coulombic efficiency is improved to 87.1%.
FIG. 3 is a diagram of the impedance of a battery formed by compounding nano silicon powder and titanium hydride powder in different proportions. Compared with a pure silicon electrode, the charge transfer resistance is obviously reduced after the titanium hydride is added, which shows that the introduction of the titanium hydride can improve the conductivity of silicon and enhance the charge transfer kinetics.
FIG. 4 is a scanning electron microscope image of the silica nanoparticles used in examples 1-4.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments 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 the invention for and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (8)
1. A preparation method of a silicon-based negative electrode material of a lithium ion battery is characterized by comprising the following steps:
1) according to the mass ratio of 8-40: 1, respectively weighing silicon powder and metal hydride powder, and putting the silicon powder and the metal hydride powder into a ball milling tank, wherein the ball-to-material ratio is 20-40: 1;
2) placing the ball milling tank on a planetary ball mill for ball milling to uniformly mix the silicon powder and the metal hydride powder;
3) putting the ball-milled dry powder into a die, and tabletting the powder on a powder tabletting machine;
4) and (3) putting the pressed sheet into a tubular furnace filled with argon, heating to 600-900 ℃, calcining for 4-8 h at the temperature, and cooling to room temperature after calcining to obtain the required silicon-based negative electrode material of the lithium ion battery.
2. The preparation method of the silicon-based negative electrode material of the lithium ion battery as claimed in claim 1, wherein the preparation method comprises the following steps: in the step 1), the silicon powder is nano silicon powder which is subjected to alcohol water milling.
3. The preparation method of the silicon-based negative electrode material of the lithium ion battery as claimed in claim 1, wherein the preparation method comprises the following steps: in step 1), the metal hydride powder includes at least one of titanium hydride, magnesium hydride, and lithium hydride powder.
4. The preparation method of the silicon-based negative electrode material of the lithium ion battery as claimed in claim 1, wherein the preparation method comprises the following steps: in the step 1), the weighing and ball milling processes are carried out in a glove box filled with argon.
5. The preparation method of the silicon-based negative electrode material of the lithium ion battery as claimed in claim 1, wherein the preparation method comprises the following steps: in the step 2), the planet ball mill performs ball milling for 6h at the speed of 300-500 r/min.
6. The preparation method of the silicon-based negative electrode material of the lithium ion battery as claimed in claim 1, wherein the preparation method comprises the following steps: in the step 3), the gauge pressure of the powder tablet press is controlled at 12MPa, and the compression time is 5 min.
7. The preparation method of the silicon-based negative electrode material of the lithium ion battery as claimed in claim 1, wherein the preparation method comprises the following steps: in the step 4), the heating rate of the tubular furnace is 2 ℃/min, and the cooling rate after the calcination is-2 ℃/min.
8. The preparation method of the silicon-based negative electrode material of the lithium ion battery as claimed in claim 1, wherein the preparation method comprises the following steps: in the step 4), the temperature is raised to 800 ℃ and then the mixture is calcined for 6 hours at the temperature.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2024044961A1 (en) * | 2022-08-30 | 2024-03-07 | 宁德时代新能源科技股份有限公司 | Negative electrode sheet, secondary battery and preparation method therefor, battery module, battery pack, and electrical device |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024044961A1 (en) * | 2022-08-30 | 2024-03-07 | 宁德时代新能源科技股份有限公司 | Negative electrode sheet, secondary battery and preparation method therefor, battery module, battery pack, and electrical device |
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