CN115057442A - Spherical micron silicon, preparation method thereof, core-shell structure composite material, electrode and battery - Google Patents

Spherical micron silicon, preparation method thereof, core-shell structure composite material, electrode and battery Download PDF

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CN115057442A
CN115057442A CN202210718959.3A CN202210718959A CN115057442A CN 115057442 A CN115057442 A CN 115057442A CN 202210718959 A CN202210718959 A CN 202210718959A CN 115057442 A CN115057442 A CN 115057442A
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CN115057442B (en
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王胜彬
杨琪
俞会根
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Beijing Weilan New Energy Technology Co ltd
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Beijing WeLion New Energy Technology Co ltd
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Abstract

The application discloses spherical micron silicon, the inside of spherical micron silicon is crystalline state silicon, and the surface is amorphous silicon, the average particle diameter D50 of spherical micron silicon is 1 ~ 8 mu m, and the sphericity is 0.7 ~ 0.95. The application also discloses a preparation method of the spherical micron silicon, a core-shell structure composite material containing the spherical micron silicon, an electrode containing the spherical micron silicon or the core-shell structure composite material, a battery containing the electrode, a circuit containing the battery and electric equipment containing the circuit.

Description

Spherical micron silicon, preparation method thereof, core-shell structure composite material, electrode and battery
Technical Field
The application relates to the technical field of lithium batteries, in particular to spherical micron silicon, a preparation method thereof, a core-shell structure composite material comprising the spherical micron silicon, an electrode and a battery.
Background
Currently, silicon materials are the most promising next-generation lithium battery negative electrode materials due to their high specific capacity. The nano-structure silicon can relieve the breakage of silicon particles to a certain extent, and becomes an important direction of current research. However, the nano silicon has the defects of high cost, poor batch stability, high activity, easy oxidation, easy agglomeration and difficult dispersion, so that the preparation of the nano silicon is difficult and the consistency is poor.
The micron silicon can solve the problems, and is gradually valued for the characteristics of low cost, simple preparation process and high first effect. However, the micron silicon obtained by mechanical crushing has an irregular shape and a surface with a plurality of edges and corners. Firstly, the existence of the edge angle is not beneficial to carrying out continuous and uniform surface coating modification on the micron silicon; moreover, the existence of the edges and corners can reduce the adhesive force of the adhesive to micron silicon, so that the powder falling of the pole piece is caused; in addition, anisotropic volume expansion during lithium intercalation in silicon is prone to failure at corners or to damage particle integrity. It can be seen that the surface modification of micron silicon and the improvement of structural stability in electrochemical processes are all problems that are currently difficult to overcome.
Disclosure of Invention
In order to solve the problems of anisotropic expansion and poor stability of a coating layer caused by excessive edges and corners of the micron silicon in the prior art and the problems of small batch preparation amount and high price of the existing micron silicon spheroidization process, the application aims to provide the spherical micron silicon with high sphericity and the sintering spheroidization process of the spherical micron silicon, so that the structural stability of the micron silicon and micron silicon composite material is effectively improved, and the micron silicon is enabled to be uniformly expanded in all directions.
The specific technical scheme of the application is as follows:
1. the spherical silicon micron is characterized in that crystalline silicon is arranged inside the spherical silicon micron, amorphous silicon is arranged on the surface of the spherical silicon micron, the average particle size D50 of the spherical silicon micron is 1-8 mu m, and the sphericity is 0.7-0.95.
2. The spherical microsilica as claimed in item 1, wherein the average particle diameter D50 of the spherical microsilica is 2 to 5 μm;
preferably, the sphericity of the spherical micron silicon is 0.8-0.95;
preferably, the specific surface area of the spherical micron silicon is 0.5-5 m 2 Preferably 1 to 4 m/g 2 /g。
3. The spherical micro silicon according to item 1 or 2, wherein the amorphous silicon has a thickness of 1 to 20nm, preferably 2 to 10 nm.
4. The preparation method of the spherical micron silicon is characterized by comprising the following steps:
and sintering, preserving heat, cooling and crushing the crystalline micron silicon in an inert atmosphere to obtain the spherical micron silicon.
5. The method according to item 4, wherein the sintering temperature is 1300 to 1600 ℃, preferably 1400 to 1500 ℃;
preferably, the temperature is increased to the sintering temperature at a temperature increase rate of 1-10 ℃/min, preferably 3-6 ℃/min;
preferably, the heat preservation time is 0.5-10 h, preferably 0.5-4 h;
preferably, the cooling rate is 10-100 ℃/min, preferably 50-80 ℃/min;
preferably, the average particle size D50 of the crystalline micron silicon is 1-8 μm, and the sphericity is 0.3-0.7;
preferably, the average particle diameter D50 of the spherical micron silicon is not higher than the average particle diameter D50 of the crystalline micron silicon;
preferably, the inert atmosphere is nitrogen or argon.
6. The method according to item 4 or 5, wherein the spherical microsilica is produced by the method according to any one of items 1 to 3.
7. A spherical microsilica obtained by the production method described in item 4 or 5.
8. The core-shell structure composite material is characterized by comprising a core material and a shell material; wherein,
the core material is the spherical micron silicon described in any one of items 1 to 3;
the shell material is selected from one or more of carbon materials, oxides and high molecular polymers.
9. The core-shell structure composite material according to item 8, wherein the carbon material is one or more selected from soft carbon, hard carbon, and graphitized carbon;
preferably, the carbon source of the carbon material is selected from one or more of asphalt, phenolic resin, humic acid, tannic acid, polymeric dopamine, polypyrrole, methane and ethane;
preferably, the oxide is selected from one or more of aluminum oxide, magnesium oxide, titanium oxide and silicon oxide;
preferably, the high molecular polymer is selected from one or two of polypyrrole and cyclized polyacrylonitrile;
preferably, the thickness of the shell material is 0.01-2 μm;
preferably, the mass ratio of the core material to the shell material is 1: 0.05-0.4.
10. An electrode, which is characterized by comprising an electrode current collector and an electrode active material layer coated on the surface of the electrode current collector, wherein the electrode active material layer comprises the spherical micron silicon in any one of items 1 to 3 and 7, or the spherical micron silicon prepared by the preparation method in item 4 or 5, or the core-shell structure composite material in item 8 or 9;
preferably, the electrode is a negative electrode.
11. A battery comprising a positive electrode, a negative electrode, a separator, and an electrolyte, wherein the negative electrode is the negative electrode of item 10.
ADVANTAGEOUS EFFECTS OF INVENTION
This application carries out the sphericization with micron silicon, for prior art's irregular micron silicon, the spherical micron silicon of this application, specific surface area reduces, the granule mobility improves, tap density improves, the follow-up technology operation degree of difficulty reduces, the inflation is more even, be favorable to forming continuous even coating and avoiding the coating to be punctured by edges and corners in the electrochemistry in-process simultaneously on the surface, improve the structural stability of micron silicon, coating among the electrochemistry process, thereby improve micron silicon combined material's electrochemical performance. Compared with the spheroidization in the prior art which is carried out by using a plasma process, the spheroidization method has the advantages of large batch preparation amount and low preparation cost by using the sintering spheroidization process.
Drawings
Fig. 1 is a TEM image of spherical microsilica according to one embodiment of the present application.
Description of the symbols
1 crystalline silicon 2 amorphous silicon
Detailed Description
The present application is described in detail below. While specific embodiments of the present application are shown below, it should be understood that the present application may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
It should be noted that throughout the specification and claims, the terms "comprises" and "comprising" are used in an open-ended fashion, and thus should be interpreted to mean "including, but not limited to. The description which follows is a preferred embodiment of the application, however, the description is made for the purpose of illustrating the general principles of the application and is not intended to limit the scope of the application. The protection scope of the present application shall be subject to the definitions of the appended claims.
1. Spherical micron silicon
On the one hand, the application provides a spherical micron silicon, the inside of spherical micron silicon is crystalline state silicon, and the surface is amorphous state silicon, spherical micron silicon's average particle diameter D50 is 1 ~ 8 mu m, and the sphericity is 0.7 ~ 0.95.
The micron silicon in the prior art is irregular crystalline silicon with a plurality of edges and corners on the surface, the crystalline silicon is anisotropic, and the anisotropic volume expansion is easy to fail or damage the integrity of particles at the edges and corners in the lithium intercalation process of silicon. The surface of the spherical micron silicon is provided with amorphous silicon with a certain thickness, the amorphous silicon is isotropic, and the isotropic expansion is in the same direction, so that the isotropic acting force of the spherical micron silicon on the coating layer on the outer side of the spherical micron silicon is uniform, and the stability of a particle structure in an electrochemical process is maintained.
The average particle size D50 of the spherical microsilica herein can be 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, 5 μm, 5.5 μm, 6 μm, 6.5 μm, 7 μm, 7.5 μm, 8 μm, etc., and the sphericity can be 0.7, 0.71, 0.72, 0.73, 0.74, 0.75, 0.76, 0.77, 0.78, 0.79, 0.80, 0.81, 0.82, 0.83, 0.84, 0.85, 0.86, 0.87, 0.88, 0.89, 0.90, 0.91, 0.92, 0.93, 0.94, 0.95, etc.
The "average particle diameter D50" in the present application refers to the particle diameter corresponding to the cumulative particle size distribution of 50% of a sample. Its physical meaning is that the particle size is less than 50% of its total amount. The particle size distribution can be measured using conventional instruments used by those skilled in the art, for example, using a laser particle size analyzer.
"sphericity" in the present application is a parameter that characterizes the morphology of a particle, the closer the particle is to a sphere in morphology, the closer its sphericity is to 1. The ratio of the surface area of a sphere of the same volume as the object to the surface area of the object is sphericity. The sphericity of the ball is equal to 1 and the sphericity of other objects is less than 1.
The sphericity formula for any particle is:
Figure BDA0003710589440000041
wherein psi is the sphericity of the particles, Vp is the volume of the particles, and Sp is the surface area of the particles.
The sphericity of the present application can be measured by the specific method given in the examples, using a dynamic image particle analyzer.
In a specific embodiment, in the spherical silicon micron, the average particle size D50 of the spherical silicon micron is 2-5 μm; the sphericity of the spherical micron silicon is 0.8-0.95.
In one embodiment, in the spherical micron silicon, the specific surface area of the spherical micron silicon is 0.5-5 m 2 Per g, for example, may be 0.5m 2 /g、1m 2 /g、1.5m 2 /g、2m 2 /g、2.5m 2 /g、3m 2 /g、3.5m 2 /g、4m 2 /g、4.5m 2 /g、5m 2 G, etc., preferably 1 to 4m 2 /g。
The specific surface area of the present application can be measured by a specific method given in examples, and is measured by a superhigh speed ratio surface area analyzer (Kubo-1200).
The spherical micron silicon has moderate particle size distribution and high sphericity, and has the advantages of lower specific surface area, higher particle fluidity and higher tap density due to the structural advantages, so that the subsequent process difficulty is reduced, and the stability of the particle structure in the electrochemical process is favorably maintained.
In one embodiment, the spherical micro-silicon of the present application has crystalline silicon inside and amorphous silicon on the surface, wherein the amorphous silicon has a thickness of 1 to 20nm, and may be, for example, 1nm, 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm, 19nm, 20nm, and the like, preferably 2 to 10 nm. The thickness of the amorphous silicon can be obtained by performing multipoint measurement and averaging through a transmission electron microscope, and can be 2 points, 3 points, 4 points, 5 points, 6 points, 7 points, 8 points, 9 points, 10 points and the like.
The structure of the spherical micron silicon is shown in a TEM image of FIG. 1, and the part of lattice fringes visible on the left side in the image is crystalline silicon 1 inside the spherical micron silicon; the right side portion without the stripe pattern is amorphous silicon 2 of the spherical micron silicon outer layer. In one embodiment, the amorphous silicon of the outer layer is 10nm thick, as shown in FIG. 1.
The inventors of the present application have found that the spherical microsilica of the present application can be easily prepared by the following preparation method. Therefore, in another aspect, the present application also provides a method for preparing spherical micron silicon, which comprises the following steps:
and sintering, preserving heat, cooling and crushing the crystalline micron silicon in an inert atmosphere to obtain the spherical micron silicon.
Here, the inert gas atmosphere may not be limited, and may be any inert gas atmosphere such as nitrogen or argon, etc.
In one embodiment, the sintering temperature is 1300 to 1600 ℃, and may be, for example, 1300 ℃, 1310 ℃, 1320 ℃, 1330 ℃, 1340 ℃, 1350 ℃, 1360 ℃, 1370 ℃, 1380 ℃, 1390 ℃, 1400 ℃, 1410 ℃, 1420 ℃, 1430 ℃, 144 ℃, 1450 ℃, 1460 ℃, 1470 ℃, 1480 ℃, 1490 ℃, 1500 ℃, 1510 ℃, 1520 ℃, 1530 ℃, 1540 ℃, 1550 ℃, 1560 ℃, 1570 ℃, 1580 ℃, 1590 ℃, 1600 ℃, and the like, preferably 1400 to 1500 ℃. The temperature is increased to be close to the melting point of the crystalline silicon, and the reaction activity of the edges is higher than that of the body, so that the edges are melted firstly, and the silicon material at the edges is recombined or transferred under the action of surface tension, so that the edges are converted into a smooth structure, and the sphericity is increased. The sintering apparatus is not limited in the present application, and any apparatus capable of raising the temperature of sintering may be used, for example, a dry rotary kiln, an electric heating furnace, a tube furnace, a box furnace, a roller kiln, or the like, or sintering may be performed using, for example, oxy-acetylene flame, oxy-hydrogen flame, or the like.
In a specific embodiment, the temperature is raised to the sintering temperature at a temperature raising rate of 1-10 ℃/min, preferably 3-6 ℃/min, for example, 1 ℃/min, 1.5 ℃/min, 2 ℃/min, 2.5 ℃/min, 3 ℃/min, 3.5 ℃/min, 4 ℃/min, 4.5 ℃/min, 5 ℃/min, 5.5 ℃/min, 6 ℃/min, 6.5 ℃/min, 7 ℃/min, 7.5 ℃/min, 8 ℃/min, 8.5 ℃/min, 9 ℃/min, 9.5 ℃/min, 10 ℃/min, etc. Also considering that a relatively low temperature rise rate increases energy consumption and time, it is preferable that the temperature rise rate is below 6 deg.C/min.
In a specific embodiment, the sintering temperature is higher than 1300 ℃, the temperature rising rate is not particularly limited in the process of rising to 1300 ℃, and when the temperature rises to 1300 ℃, the temperature starts to rise to the sintering temperature at the temperature rising rate of 1-10 ℃/min, preferably 3-6 ℃/min. When the temperature rises to 1300 ℃, the temperature rise rate needs to be adjusted to ensure that the temperature rise rate is not too fast, the phenomenon that particles are adhered due to quick melting of silicon edges and corners is avoided, although the adhesion can be opened through crushing, the edges and corners can be caused in the crushing process.
In a specific embodiment, the heat preservation time is 0.5 to 10 hours, for example, 0.5 hour, 1 hour, 1.5 hour, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours, 10 hours, and the like, preferably 0.5 to 4 hours. The heat preservation time is too short, the edges and corners are not fully melted, and the sphericity is not high; if the holding time is too long, the corners are sufficiently melted and contact transfer may occur between the particles, resulting in sticking. Meanwhile, considering that the relatively high heat preservation time increases energy consumption and time, the heat preservation time is preferably less than or equal to 4 hours.
In a specific embodiment, the cooling rate is 10-100 ℃/min, for example, 10 ℃/min, 15 ℃/min, 20 ℃/min, 25 ℃/min, 30 ℃/min, 35 ℃/min, 40 ℃/min, 45 ℃/min, 50 ℃/min, 55 ℃/min, 60 ℃/min, 65 ℃/min, 70 ℃/min, 75 ℃/min, 80 ℃/min, 85 ℃/min, 90 ℃/min, 95 ℃/min, 100 ℃/min, etc., preferably 50-80 ℃/min. And controlling the cooling rate to form a layer of amorphous silicon by crystal form dislocation, and controlling the cooling rate to be 10-100 ℃/min to enable the thickness of the amorphous silicon to reach 1-20 nm. Further, since the load on the equipment is increased as the temperature decrease rate is increased, the temperature decrease rate is more preferably 80 ℃/min or less. The cooling device or method is not limited in the present application, and any device or method capable of cooling may be used, for example, a method of purging a low-temperature inert atmosphere may be used.
The crystalline microsilica of the present application is state of the art crystalline silicon. In one embodiment, the average particle diameter D50 of the crystalline microsilica is 1-8 μm, such as 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, 5 μm, 5.5 μm, 6 μm, 6.5 μm, 7 μm, 7.5 μm, 8 μm, etc., and the sphericity of the crystalline microsilica is 0.3-0.7, such as 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, etc. The average particle diameter D50 of the spherical micron silicon is less than or equal to the average particle diameter D50 of the crystalline micron silicon, and the sphericity of the spherical micron silicon is greater than that of the crystalline micron silicon.
In one embodiment, the preparation method of the present application is a preparation method of any one of the aforementioned spherical micron silicon.
In yet another aspect, the present application further provides a spherical micron silicon prepared by any one of the preparation methods.
2. Core-shell structure composite material
In addition, the application also provides a core-shell structure composite material, which comprises a core material and a shell material; wherein the core material is any one of the spherical micron silicon; the shell material is selected from one or more of carbon materials, oxides and high molecular polymers. The core material forms a core of a core-shell structure, and the shell material forms a shell of the core-shell structure.
When the core-shell structure composite material comprising the spherical micron silicon is applied to the lithium ion battery, the spherical micron silicon expands isotropically, the spherical structure improves the continuity of surface coating, the stress of a coating layer is uniform during expansion, and the composite material overcomes the huge expansion effect of the micron silicon, so that the deformation of the battery in the circulating process is reduced, and the safety performance of the battery is improved. Meanwhile, the composite material keeps structural stability in the circulation process, and growth of an interface irreversible SEI film and permeation of electrolyte are avoided, so that the circulation performance of the battery is improved.
In a specific embodiment, in the core-shell structure composite material of the present application, the carbon material is selected from one or two or more of soft carbon, hard carbon, and graphitized carbon.
The term "soft carbon" in the present application means carbon having a high degree of graphitization when the heat treatment temperature reaches the graphitization temperature. Coke, graphitized Mesophase Carbon Microbeads (MCMB), carbon fibers, etc. are commonly used.
The term "hard carbon" as used herein means carbon that is difficult to graphitize and is a thermal decomposition product of a high molecular polymer. The hard carbon can be obtained by thermally decomposing the crosslinking resin with a special structure at about 1000 ℃. Such carbon is hard to graphitize even at a high temperature of 2500 ℃ or higher, and common hard carbons include resin carbon, carbon black, and the like.
The "graphitized carbon" in the present application means carbon having a high graphitization degree obtained by subjecting the above-mentioned soft carbon or hard carbon to graphitization catalysis by a catalyst.
The carbon source of the carbon material of the present application is not limited, and may be any carbon source, for example, one or more selected from the group consisting of pitch, phenol resin, humic acid, tannic acid, polymeric dopamine, polypyrrole, methane, and ethane; the oxide of the application can be selected from one or more than two of aluminum oxide, magnesium oxide, titanium oxide and silicon oxide; the high molecular polymer in the present application may be selected from one or both of polypyrrole and cyclized polyacrylonitrile.
In one embodiment, the shell material has a thickness of 0.01 to 2 μm, for example, 0.01 μm, 0.1 μm, 0.3 μm, 0.5 μm, 0.7 μm, 0.9 μm, 1 μm, 1.2 μm, 1.4 μm, 1.6 μm, 1.8 μm, 2 μm, and the like, preferably 0.01 to 1.5 μm. In this application, the thickness of the shell material can be measured by a transmission electron microscope.
In a preferred embodiment, the shell material comprises a soft material and a hard material in sequence from the core to the shell, wherein the soft material is selected from one or more of soft carbon, hard carbon and high polymer, and the hard material is selected from one or two of oxide and graphitized carbon.
Micron silicon is very easy to break in the electrochemical process due to the size of the micron silicon, and the breaking of the micron silicon is difficult to inhibit by simple coating. Therefore, more than two coating layers with different structures can be preferably used for matching, and the volume expansion of the micron silicon is relieved and the circulation stability is improved by utilizing the combination of soft and hard coating materials.
In a specific embodiment, in the core-shell structure composite material of the present application, the mass ratio of the core material to the shell material is 1:0.05 to 0.4, and may be, for example, 1:0.05, 1:0.1, 1:0.15, 1:0.2, 1:0.25, 1:0.3, 1:0.35, or 1: 0.4. The mass ratio of the two is controlled within the range, and the optimal comprehensive orientation among the cycle performance, the first coulombic efficiency and the specific capacity can be realized.
In one embodiment, the shell material comprises a carbon material, which may be coated with a carbon source in a liquid or solid phase and then sintered, or coated directly by vapor deposition to provide a shell material comprising a carbon material.
In one embodiment, the shell material comprises an oxide, and the shell material comprising the oxide is obtained by coating an oxide source by hydrolysis or evaporation and then sintering.
3. Electrode for electrochemical cell
In another aspect, the present application further provides an electrode, including an electrode current collector and an electrode active material layer coated on the electrode current collector, wherein the electrode active material layer at least contains spherical micron silicon as an electrode active material, and the spherical micron silicon is any one of the spherical micron silicon or spherical micron silicon prepared by any one of the preparation methods of the present application. The electrode active material layer may further include any of the core-shell structure composite materials described previously in this application. The electrode of the present application is preferably a negative electrode.
3.1. Electrode active material
The electrode active material in the present application may be a negative electrode active material, and a negative electrode active material generally used in the art may be used.
Preferably, the electrode active material has the spherical micro silicon of the present application as a main component.
The electrode active material layer may contain other electrode active materials in addition to the spherical micro silicon of the present application. Hereinafter, other electrode active materials will be described.
Examples of the negative electrode active material include: examples of the carbon material include graphite (natural graphite, artificial graphite, and the like) as high-crystalline carbon, low-crystalline carbon (soft carbon), hard carbon, carbon Black (Ketjen Black (registered trademark), acetylene Black, channel Black, lamp Black, oil furnace Black, thermal Black, and the like), fullerene, carbon nanotubes, carbon nanofibers, carbon nanohorns, carbon fibrils, and the like. Examples of the negative electrode active material include Si, Ge, Sn, Pb, Al, In, Zn, H, Ca, Sr, Ba, Ru, Rh, Ir, Pd, Pt, Cu, Mo, Cu, Sn, Cu, Sn, Ag, Cu, Sn, Cu, and Sn, Cu, and Cu,Ag. Simple substances of elements such as Au, Cd, Hg, Ga, Tl, C, N, Sb, Bi, O, S, Se, Te, and Cl, which are alloyed with lithium, and oxides and carbides containing these elements. Examples of such oxides include silicon monoxide (SiO) and SiO x (0<x<2) Tin dioxide (SnO) 2 )、SnO x (0<x<2)、SnSiO 3 Examples of the carbide include silicon carbide (SiC). Further, as the negative electrode active material, a metal material such as lithium metal, a lithium-titanium composite oxide (for example, lithium titanate Li) and the like can be mentioned 4 Ti 5 O 12 ) And the like lithium-transition metal composite oxides. However, the material is not limited to these materials, and conventionally known materials that can be used as a negative electrode active material for a lithium ion battery can be used. These negative electrode active materials may be used alone or in combination of two or more.
3.2. Electrode current collector
The electrode current collector of the present application may be a negative electrode current collector, which is composed of a conductive material. The thickness of the electrode current collector is not particularly limited. The thickness of the electrode current collector is usually about 0.1 to 1000 μm, preferably about 1 to 100 μm. The shape of the electrode current collector is not particularly limited. There is no particular limitation on the material constituting the electrode current collector. For example, it may be copper.
3.3. Electrode for electrochemical cell
The electrode may be prepared by forming the active material layer on the electrode current collector using a conventionally known method, but is not limited thereto. One skilled in the art can select an appropriate method for manufacturing the electrode according to the type of battery to be manufactured.
The electrode using the electrode active material can be manufactured by a conventional method. That is, the electrode can be obtained by dry-mixing an electrode active material, a conductive agent, and a binder and a thickener used as needed to form a sheet, pressing the sheet material onto an electrode current collector, or dissolving or dispersing these materials in a liquid medium to form a slurry, applying the slurry onto the electrode current collector, and drying the slurry to form an electrode active material layer on the electrode current collector.
As the conductive agent, any other component that can be used as a conductive agent may be contained. For example, it may include: metal materials such as copper and nickel; natural graphite, artificial graphite, and other graphite; carbon black such as acetylene black; and carbon materials such as amorphous carbon such as needle coke. These conductive agents may be used alone, or two or more of them may be used in combination in any combination and ratio.
In addition, the electrode active material layer may further include a binder. The binder used for producing the electrode active material layer is not particularly limited, and when a coating method is used, it may be any material that can be dissolved or dispersed in a liquid medium used for producing the electrode.
The solvent used for forming the slurry is not particularly limited as long as it can dissolve or disperse the electrode active material, the conductive agent, the binder, and the thickener used as needed, and any solvent of an aqueous solvent and an organic solvent can be used.
Thickeners are commonly used to adjust the viscosity of the slurry. The electrode active material layer may further include a thickener. The thickener is not particularly limited.
4. Battery with a battery cell
The electrodes of the present application may be used in batteries. In another aspect, therefore, the present application also provides a battery comprising a positive electrode, a negative electrode, a separator, and an electrolyte, wherein the negative electrode is the negative electrode described previously herein.
A battery in this application refers to a single physical module that includes one or more battery cells to provide higher voltage and capacity. For example, the battery referred to in the present application may include a battery module or a battery pack, etc.
The battery cell of the present application may include one or more of a lithium ion secondary battery, a lithium ion primary battery, a lithium sulfur battery, a sodium lithium ion battery, a sodium ion battery, and a magnesium ion battery, which is not limited in the present application. The battery cell of the present application may be in a cylindrical shape, a flat body, a rectangular parallelepiped shape, or other shapes, and the embodiment of the present application does not limit this. The battery cells are generally divided into three types in an encapsulation manner: the battery pack includes a cylindrical battery cell, a square battery cell, and a pouch battery cell, to which the present application is not limited.
The separator is generally disposed between the positive electrode and the negative electrode. The material and shape of the separator are not particularly limited, and a known separator can be arbitrarily used. For example, a porous sheet or a nonwoven fabric-like material having excellent liquid retention properties can be used, preferably, a resin, glass fiber, or an inorganic material.
An electrolyte is filled between the positive electrode and the negative electrode. The electrolyte may be an aqueous electrolyte or a non-aqueous electrolyte. In addition, the electrolyte may be an electrolytic solution, a polymer gel electrolyte, or a solid polymer electrolyte.
Examples
The materials used in the tests and the methods of the tests are generally and/or specifically described in the present application, and in the following examples, the reagents or instruments used are not indicated by the manufacturer, but are all conventional reagents or instruments commercially available.
Example 1
(1) 1kg of crystalline silicon micron with D50 of 5 μm and sphericity of 0.3 is heated to 1400 ℃ at a speed of 5 ℃/min under nitrogen atmosphere, and after heat preservation is carried out for 5h, the crystalline silicon micron is cooled to room temperature at a speed of 50 ℃/min, and then taken out and crushed to obtain the spherical silicon micron with D50 of 4 μm and sphericity of 0.8, which is marked as sample 1.
(2) Adding 1kg of sample 1 into an ethanol solution of tetrabutyl titanate containing 1 wt% of Ti, slowly dropwise adding deionized water to fully hydrolyze the tetrabutyl titanate, heating and evaporating to dryness, and sintering the product at 800 ℃ for 2 hours in a nitrogen atmosphere to obtain the coated TiO 2 Is designated as sample 2.
(3) 1kg of sample 2 was mixed well with 100g of bitumen and mechanically fused. And sintering the obtained sample at 800 ℃ for 4h in a nitrogen atmosphere to obtain the final product, namely the spherical micron silicon composite material.
Example 2
(1) Heating crystalline micron silicon with the sphericity of 0.5 and the diameter of 6 microns of 1kgD50 to 1500 ℃ at the speed of 10 ℃/min in nitrogen atmosphere, keeping the temperature for 2 hours, cooling to room temperature at the speed of 100 ℃/min, taking out, crushing to obtain spherical micron silicon with the diameter of 6 microns of D50 and the sphericity of 0.9, and marking as a sample 1.
(2) Adding 1kg of sample 1 into 20 wt% of phenolic resin ethanol solution, heating and evaporating to dryness, and sintering the product at 900 ℃ for 2h in a nitrogen atmosphere to obtain spherical micron silicon coated with a carbon material, which is recorded as sample 2.
(3) 1kg of sample 2 was added to an aluminum nitrate solution containing 2 wt% Al, and heated, stirred and evaporated to dryness. And sintering the obtained sample at 600 ℃ for 4h in a nitrogen atmosphere to obtain the final product, namely the spherical micron silicon composite material.
Example 3
(1) 1kg of crystalline silicon micron with D50 of 2 μm and sphericity of 0.6 is heated to 1400 ℃ at 3 ℃/min under nitrogen atmosphere, and after heat preservation for 4h, the temperature is reduced to room temperature at the speed of 60 ℃/min, and the crystalline silicon micron is taken out and crushed to obtain the spherical silicon micron with D50 of 2 μm and sphericity of 0.95, which is marked as sample 1.
(2) Adding 1kg of sample 1 into a buffer solution with the pH value of 9, adding 10 wt% of tannic acid after uniform dispersion, stirring for 24 hours, and performing suction filtration and drying. And sintering the product at 1000 ℃ for 2h in a nitrogen atmosphere to obtain the spherical micron silicon coated with the carbon material, and recording as a sample 2.
(3) 1kg of sample 2 was added to a DMF solution containing 5% by weight of polyacrylonitrile and stirred to dryness. And heating the obtained material to 350 ℃ under nitrogen, and reacting for 5 hours to obtain the final product, namely the spherical micron silicon composite material.
Example 4
(1) Heating crystalline silicon micron with the sphericity of 0.3 and the diameter of 4 microns of 1kgD50 to 1450 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, preserving the temperature for 5h, cooling to room temperature at the speed of 80 ℃/min, taking out, crushing to obtain spherical silicon micron with the diameter of 0.8 and the diameter of 3 microns of D50, and marking as a sample 1.
(2) 1kg of sample 1 was mixed well with 200g of bitumen and mechanically fused. The resulting sample was sintered at 800 ℃ for 4h under a nitrogen atmosphere and was designated sample 2.
(3) Dispersing 1kg of sample 2 in a buffer solution with the pH value of 8.5, adding 50g of dopamine hydrochloride, stirring for reaction for 6 hours, filtering and drying. And sintering the dried product at 900 ℃ under nitrogen for 3h to obtain the final product of the spherical micron silicon composite material.
Example 5
This example differs from example 3 in that the sintering temperature was 1600 ℃.
Example 6
This example differs from example 3 in that the sintering temperature was 1300 ℃.
Example 7
This example differs from example 3 in that the sintering temperature was 1500 ℃.
Example 8
This example differs from example 3 in that the temperature increase rate was 1 ℃/min.
Example 9
This example is different from example 3 in that the temperature increase rate was 10 ℃/min.
Example 10
This example differs from example 3 in that the incubation time was 0.5 h.
Example 11
This example differs from example 3 in that the incubation time was 10 h.
Example 12
This example differs from example 3 in that the cooling rate was 10 ℃/min.
Example 13
The present example is different from example 3 in that the cooling rate is 100 deg.C/min.
Example 14
This example differs from example 3 in that the cooling rate was 50 ℃/min.
Example 15
This example differs from example 3 in that the cooling rate was 80 ℃/min.
Comparative example 1
(1) Adding 1kg of crystalline micrometer silicon with D50 of 1 μm and sphericity of 0.6 into buffer solution with pH of 9, dispersing uniformly, adding 10 wt% tannin, stirring for 24h, filtering, and drying. And sintering the product at 1000 ℃ for 2h in a nitrogen atmosphere to obtain the spherical micron silicon coated with the carbon material, and recording as a sample 2.
(2) 1kg of sample 2 was added to a DMF solution containing 5% by weight of polyacrylonitrile and stirred to dryness. And heating the obtained material to 350 ℃ under nitrogen, and reacting for 5h to obtain the final product, namely the spherical micron silicon composite material.
The parametric conditions, reagents, sample parameters, etc. for each example are set forth in tables 1 and 2 below:
TABLE 1
Figure BDA0003710589440000141
TABLE 2
Figure BDA0003710589440000142
Experimental example 1 preparation and Performance test of lithium batteries
The spherical micro-silicon composite materials (90 wt%) obtained in examples 1-15 and comparative example 1 were mixed with conductive agent (1 wt% CNT and 3 wt% SP), binder (4 wt% CMC and 2 wt% SBR) and deionized water to form slurry, which was coated, dried and cut to obtain a lithium electrode sheet, wherein "wt%" represents the percentage of each component in the total weight of the core-shell structure composite material, the conductive agent and the binder. Assembling a lithium electrode plate and a conventional electrolyte into a button type half cell, and carrying out charge and discharge tests under the following test conditions: the voltage range of 5mV-0.8V is activated for 2 cycles at 0.1C/0.1C, and the cycle is performed at 0.3C/0.3C. The electrochemical performance parameters of the cells fabricated with the materials of examples 1-15 and comparative example 1 were tested as shown in table 3 below.
TABLE 3
Numbering First reversible specific capacity First coulombic efficiency Retention ratio of 50 cycles
Example 1 2764 88.5 76
Example 2 2812 89.6 62
Example 3 2796 89.8 94
Example 4 2803 88.9 71
Example 5 2726 88.1 84
Example 6 2740 88.4 79
Example 7 2741 88.8 82
Example 8 2764 89.5 92
Example 9 2747 88.1 82
Example 10 2732 88.0 71
Example 11 2785 89.6 93
Example 12 2749 88.2 84
Example 13 2772 89.2 92
Example 14 2766 89.9 94
Example 15 2770 89.8 94
Comparative example 1 2824 88.7 58
The foregoing is directed to preferred embodiments of the present application, other than the limiting examples of the present application, and variations of the present application may be made by those skilled in the art using the foregoing teachings. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present application still belong to the protection scope of the technical solution of the present application.

Claims (11)

1. The spherical silicon micron is characterized in that crystalline silicon is arranged inside the spherical silicon micron, amorphous silicon is arranged on the surface of the spherical silicon micron, the average particle size D50 of the spherical silicon micron is 1-8 mu m, and the sphericity is 0.7-0.95.
2. The spherical microsilica as claimed in claim 1, wherein the average particle size D50 is 2-5 μm;
preferably, the sphericity of the spherical micron silicon is 0.8-0.95;
preferably, the specific surface area of the spherical micron silicon is 0.5-5 m 2 Preferably 1 to 4 m/g 2 /g。
3. The spherical microsilica as claimed in claim 1 or 2, wherein the amorphous silicon has a thickness of 1 to 20nm, preferably 2 to 10 nm.
4. The preparation method of the spherical micron silicon is characterized by comprising the following steps:
and sintering, preserving heat, cooling and crushing the crystalline micron silicon in an inert atmosphere to obtain the spherical micron silicon.
5. The method of claim 4, wherein the sintering temperature is 1300-1600 ℃, preferably 1400-1500 ℃;
preferably, the temperature is increased to the sintering temperature at a temperature increase rate of 1-10 ℃/min, preferably 3-6 ℃/min;
preferably, the heat preservation time is 0.5-10 h, preferably 0.5-4 h;
preferably, the cooling rate is 10-100 ℃/min, preferably 50-80 ℃/min;
preferably, the average particle size D50 of the crystalline micron silicon is 1-8 μm, and the sphericity is 0.3-0.7;
preferably, the average particle diameter D50 of the spherical micron silicon is not higher than the average particle diameter D50 of the crystalline micron silicon;
preferably, the inert atmosphere is nitrogen or argon.
6. The method according to claim 4 or 5, wherein the method is the method according to any one of claims 1 to 3.
7. A spherical microsilica obtained by the production method of claim 4 or 5.
8. The core-shell structure composite material is characterized by comprising a core material and a shell material; wherein,
the core material is the spherical micron silicon as set forth in any one of claims 1 to 3;
the shell material is selected from one or more of carbon materials, oxides and high molecular polymers.
9. The core-shell structure composite material according to claim 8, wherein the carbon material is one or more selected from soft carbon, hard carbon, and graphitized carbon;
preferably, the carbon source of the carbon material is selected from one or more of asphalt, phenolic resin, humic acid, tannic acid, polymeric dopamine, polypyrrole, methane and ethane;
preferably, the oxide is selected from one or more of aluminum oxide, magnesium oxide, titanium oxide and silicon oxide;
preferably, the high molecular polymer is selected from one or two of polypyrrole and cyclized polyacrylonitrile;
preferably, the thickness of the shell material is 0.01-2 μm;
preferably, the mass ratio of the core material to the shell material is 1: 0.05-0.4.
10. An electrode, comprising an electrode current collector and an electrode active material layer coated on the surface of the electrode current collector, wherein the electrode active material layer comprises the spherical micron silicon according to any one of claims 1 to 3 and 7, or the spherical micron silicon prepared by the preparation method according to claim 4 or 5, or the core-shell structure composite material according to claim 8 or 9;
preferably, the electrode is a negative electrode.
11. A battery comprising a positive electrode, a negative electrode, a separator, and an electrolyte, wherein the negative electrode is the negative electrode according to claim 10.
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