CN109980191B - High-coulombic-efficiency silicon-carbon negative electrode material and preparation method and application thereof - Google Patents
High-coulombic-efficiency silicon-carbon negative electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of battery cathode materials, in particular to a high coulombic efficiency silicon-carbon cathode material and a preparation method and application thereof, which are characterized by comprising the following steps: mixing raw materials, carrying out redox reaction, crushing treatment and vapor deposition to obtain a finished product. Compared with the prior art, the reduction degree of the silicon monoxide can be controlled by regulating and controlling the addition amount of the reducing agent; the conductivity of the material obtained by the invention is close to that of graphite, the silicon nanoparticles and the uniform buffer structure with controllable content are arranged in the particles, the first coulombic efficiency is more than 87%, the specific capacity is more than 1400mAh/g, the defect of low first efficiency of the silicon oxide material is overcome, and the material has a good application prospect.
Description
Technical Field
The invention relates to the technical field of battery cathode materials, in particular to a high-coulombic-efficiency silicon-carbon cathode material and a preparation method and application thereof.
Background
The novel high-capacity power battery cathode material can be developed and researched to solve the problem of short endurance mileage of the conventional Electric Vehicle (EV), and is favorable for further popularization of new energy vehicles. Since Si has a high theoretical lithium intercalation capacity (about 4200mAh/g) and a moderate lithium intercalation/deintercalation potential, research on Si as a lithium storage matrix has become a hot spot for developing a negative electrode material. The major problems of powdered silicon currently used as an electrode active material are its poor conductivity and severe volume effects, resulting in poor charge and discharge stability. The silica material contains silicon oxide and Li generated in the process of lithium intercalation4SiO4Can be used as a buffer substance, and thus the cycle characteristic of the silicon material as a negative electrode material is considered to be better than that of pure silicon. However, the reaction of the silicon oxide with lithium ions consumes a part of lithium in the positive electrode, and therefore, the efficiency is low for the first time.
The Chinese patent application with the publication number of 107195895A discloses a method for obtaining a silicon-based material by heating magnesium and aluminum alloy serving as reducing agents and starting from a silicon dioxide molecular sieve (one of MCM-41, MCM-48, MCM-50 and SBA-15) and carrying out a reduction reaction. However, the raw material is silicon dioxide, and the reduction degree, the phase composition after reduction and the distribution uniformity of silicon are difficult to control; the material obtained by the preparation method does not substantially solve the problems that the silicon material has poor conductivity and volume expansion effect and is difficult to be directly applied to a lithium ion battery system; starting from porous molecular sieves, the cost is high.
In order to industrially apply SiOx as a high-capacity negative electrode material, a modification method for the material is urgently needed at present, which can reduce the irreversible reaction of a silicon-oxygen negative electrode in the charging and discharging processes and further improve the first coulombic efficiency.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, the reduction degree of the silicon oxide is controlled by regulating the addition amount of a reducing agent by using the silicon oxide as a precursor so as to adjust the structure of the material, so that the electrochemical performance is improved, and the conductive characteristic of the particles is further optimized by coating with vapor deposition carbon after crushing, so that the silicon-carbon cathode material with high first coulombic efficiency is prepared.
In order to achieve the aim, the method for designing the high-coulombic-efficiency silicon-carbon negative electrode material is characterized by comprising the following steps of:
step one, mixing raw materials: selecting SiOx with the average particle size of 1-20 mu m and the purity of more than 99.9%; 0.2-20 mu m of alloy powder with the purity of more than 99.9 percent and used as a reducing agent, and the alloy powder are fully and uniformly mixed; wherein the addition amount of the alloy powder is 1-20 wt%;
step two, oxidation-reduction reaction: transferring the mixed raw materials into an atmosphere furnace, heating to 400-900 ℃ at a speed of 1-10 ℃/min under the protection of inert gas, reacting for 2-24 hours, and naturally cooling to room temperature to obtain a silicon alloy material;
step three, crushing treatment: pickling the obtained silicon alloy material to remove redundant alloy powder, and then crushing to obtain silicon alloy material particles with the particle size of 2-10 um;
step four, vapor deposition: selecting any one of methane, ethylene, acetylene, propanol and isopropanol as a carbon source according to the final deposited carbon content of 0.5-10 wt%, carrying out vapor deposition reaction on the surface of the silicon alloy material particles at the temperature of 400-900 ℃, such as 450 ℃ and 600 ℃ for 2-12 hours, such as 1 hour, 3 hours and 10 hours, by taking inert gas as carrier gas, and naturally cooling to room temperature to obtain the finished product.
The silicon oxide in the raw material adopts micron-sized and amorphous structure micron-sized; the alloy powder is in a micron-sized particle size, and the particle size of the alloy powder is 1/3-1/5 of the particle size of the silicon oxide.
The alloy powder is one or any combination of aluminum alloy, titanium alloy and magnesium alloy;
the aluminum alloy is any one of aluminum nickel, aluminum silicon, aluminum sodium and aluminum iron;
the titanium alloy is any one of alpha titanium alloy, beta titanium alloy and alpha + beta titanium alloy;
the magnesium alloy is any one of magnesium aluminum, magnesium zinc and magnesium lithium.
And the mixing in the step one is grinding in a ball mill for 1-10 h. E.g., 1,2,3,5, or 10h, etc.
The atmosphere in the oxidation-reduction reaction adopts a furnace vertical or horizontal box furnace, and the oxygen content is controlled to be less than 20ppm in the heat treatment process; in the oxidation-reduction reaction, gas is firstly vacuumized and replaced for 3-5 times, and then heating is started.
And in the third step, hydrochloric acid or nitric acid is adopted for acid washing.
In the fourth step, the content of the carbon source gas in the vapor deposition is 5-30%, and the flow rate is 5-100 sccm.
And testing the oxygen content of the silicon oxide SiOx in the initial raw material and the oxygen content in the silicon alloy material obtained after the redox reaction by using an oxygen content analyzer as a tool, and determining the reduction degree of the silicon oxide SiOx by calculating the x value before and after the reaction.
The silicon-carbon negative electrode material prepared by the method is characterized in that silicon nanoparticles and a uniform buffer structure with controllable content are arranged inside, the first coulombic efficiency is more than 87%, and the specific capacity is more than 1400 mAh/g.
The application of the silicon-carbon negative electrode material is characterized in that the silicon-carbon negative electrode material is used as a multiplying power type lithium ion battery negative electrode material or a capacity type lithium ion negative electrode material.
Compared with the prior art, the reduction degree of the silicon monoxide can be controlled by regulating and controlling the addition amount of the reducing agent; the conductivity of the material obtained by the invention is close to that of graphite, the silicon nanoparticles and the uniform buffer structure with controllable content are arranged in the particles, the first coulombic efficiency is more than 87%, the specific capacity is more than 1400mAh/g, the defect of low first efficiency of the silicon oxide material is overcome, and the material has a good application prospect.
Drawings
FIG. 1 is an SEM photograph of a sample obtained in example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further described below by using specific examples, but the scope of the present invention is not limited thereto.
The inert gas used in the oxidation-reduction reaction in the invention is one or a combination of nitrogen and argon.
In the vapor deposition, the inert gas is one or a combination of nitrogen and argon.
Example 1
Selecting silicon monoxide with the average grain diameter of 4 mu m (the purity is more than 99.9 percent) and aluminum-silicon alloy powder with the average grain diameter of 1 mu m (the purity is more than 99.9 percent), adding 1 weight percent of alloy, and fully and uniformly mixing the silicon dioxide with the aluminum-silicon alloy powder;
transferring the mixture into an atmosphere furnace, heating the mixture to 700 ℃ at the speed of 5 ℃/min, reacting the mixture for 20 hours, and naturally cooling the mixture to room temperature;
pickling the obtained silicon alloy material with one of hydrochloric acid or nitric acid to remove redundant metal aluminum, and then carrying out ball milling to obtain particles with the particle size of 2 microns;
and (3) transferring the particles into a CVD furnace, heating to 700 ℃ at the speed of 5 ℃/min under the protection of argon, switching to ethylene/argon mixed gas with the ethylene content of 10%, wherein the flow rate is 30sccm, switching to argon at the flow rate of 50sccm after reacting for 30 minutes, and cooling to room temperature to obtain a finished product, wherein the finished product is shown in figure 1.
Example 2
Selecting silicon monoxide with the average grain diameter of 4 mu m (the purity is more than 99.9 percent) and aluminum-silicon alloy powder with the average grain diameter of 1 mu m (the purity is more than 99.9 percent), adding 5 percent by weight of alloy, and fully and uniformly mixing the silicon dioxide with the aluminum-silicon alloy powder;
transferring the mixture into an atmosphere furnace, heating the mixture to 700 ℃ at the speed of 5 ℃/min, reacting the mixture for 20 hours, and naturally cooling the mixture to room temperature;
pickling the obtained silicon alloy material with one of hydrochloric acid or nitric acid to remove redundant metal aluminum, and then carrying out ball milling to obtain particles with the particle size of 2 microns;
and (3) transferring the particles into a CVD furnace, heating to 700 ℃ at the speed of 5 ℃/min under the protection of argon, switching to ethylene/argon mixed gas with the ethylene content of 10%, wherein the flow rate is 30sccm, reacting for 30 minutes, switching to argon at the flow rate of 50sccm, and cooling to room temperature to obtain a finished product.
Example 3
Selecting silicon monoxide with the average grain diameter of 2 mu m (the purity is more than 99.9 percent) and aluminum-silicon alloy powder with the average grain diameter of 1 mu m (the purity is more than 99.9 percent), fully and uniformly mixing the silicon dioxide with the aluminum-silicon alloy powder according to the addition of 5 weight percent of alloy;
transferring the mixture into an atmosphere furnace, heating the mixture to 700 ℃ at the speed of 5 ℃/min, reacting the mixture for 20 hours, and naturally cooling the mixture to room temperature;
pickling the obtained silicon alloy material with one of hydrochloric acid and nitric acid to remove redundant metal aluminum; then, carrying out ball milling to obtain particles with the particle size of 2 mu m;
transferring the particles into a CVD furnace, heating to 700 ℃ at a speed of 5 ℃/min under the protection of argon, switching to ethylene/argon mixed gas with the ethylene content of 10%, wherein the flow rate is 30sccm, reacting for 30 minutes, switching to argon at a flow rate of 50sccm, and cooling to room temperature to obtain a finished product;
example 4
Selecting silicon oxide with the average grain diameter of 4 mu m (the purity is more than 99.9 percent) and alpha titanium alloy powder with the average grain diameter of 1 mu m (the purity is more than 99.9 percent), adding 1 weight percent of alloy, and fully and uniformly mixing the silicon oxide with the alpha titanium alloy powder;
transferring the mixture into an atmosphere furnace, heating the mixture to 900 ℃ at the speed of 5 ℃/min, reacting the mixture for 20 hours, and naturally cooling the mixture to room temperature;
pickling the obtained silicon alloy material with hydrochloric acid or nitric acid to remove redundant metal aluminum, and then performing ball milling to obtain particles with the particle size of 2 mu m;
and (3) transferring the particles into a CVD furnace, heating to 700 ℃ at the speed of 5 ℃/min under the protection of argon, switching to ethylene/argon mixed gas with the ethylene content of 10%, wherein the flow rate is 30sccm, reacting for 90 minutes, switching to argon at the flow rate of 50sccm, and cooling to room temperature to obtain a finished product.
The final silicon-carbon composite materials obtained in the embodiments 1,2,3 and 4 are respectively used as the button type lithium ion battery cathode active materials, and the preparation steps are as follows:
1. material proportioning and stirring: stirring the active substances, namely CMC and SBR (80: 10:5: 5), to obtain thick slurry;
2. coating the slurry on a copper foil to manufacture a pole piece, rolling after coating, and then baking at 120 ℃ for 4 hours;
3. assembling the battery: the button cell is assembled by adding electrolyte into the lithium sheet as the negative electrode and the polypropylene as the diaphragm.
An Aribin test cabinet is adopted, the voltage range is 0.01-1.5V, and the multiplying power is 0.1C/0.5C to evaluate the electrochemical performance of the material. The results of the power-on test using the materials obtained in examples 1,2,3 and 4 are shown in Table 1.
Table 1. oxygen content and electrification test results for samples obtained in examples 1 and 2.
(a) FDC for first lithium insertion capacity, FCC for first lithium removal capacity, ICE for first coulombic efficiency;
(b) OC means the oxygen content (mass percent) in the resulting sample as measured by leco.on836;
(c) x denotes the value of x in SiOx, calculated by: x is 28OC/16/(1-OC), and the raw material x before treatment is 0.92;
(d) the resulting degree of reduction is calculated by the value of x.
In the present invention, if x in the starting SiOx is 0.9 and x after reduction is 0.7, the degree of reduction is 22.2%, and the higher the degree of reduction, the lower the oxygen content in the treated sample.
The silicon-carbon cathode material prepared by the invention can obtain materials with different reduction degrees by adjusting the proportion of the initial silicon monoxide and the alloy powder to be used as the cathode material of the capacity type lithium ion battery.
Various changes, modifications, substitutions and alterations to the specific embodiments without departing from the technical principles and spirit of the present invention are to be regarded as equivalents of the claims, which are defined by the scope of the claims.
Claims (9)
1. A method for preparing a high-coulombic-efficiency silicon-carbon negative electrode material is characterized by comprising the following steps:
step one, mixing raw materials: selecting SiOx with the average particle size of 1-20 mu m and the purity of more than 99.9%; 0.2-20 mu m of alloy powder with the purity of more than 99.9 percent and used as a reducing agent, and the alloy powder are fully and uniformly mixed; wherein the addition amount of the alloy powder is 1-20 wt%; the alloy powder is aluminum silicon or alpha titanium alloy;
step two, oxidation-reduction reaction: transferring the mixed raw materials into an atmosphere furnace, heating to 400-900 ℃ at a speed of 1-10 ℃/min under the protection of inert gas, reacting for 2-24 hours, and naturally cooling to room temperature to obtain a silicon alloy material;
step three, crushing treatment: pickling the obtained silicon alloy material to remove redundant alloy powder, and then crushing to obtain silicon alloy material particles with the particle size of 2-10 um;
step four, vapor deposition: selecting any one of methane, ethylene, acetylene, propanol and isopropanol as a carbon source, taking inert gas as carrier gas to perform vapor deposition reaction on the surface of the silicon alloy material particles at the temperature of 400-900 ℃ for 2-12 hours, and naturally cooling to room temperature to obtain the finished product, wherein the content of the final deposited carbon is 0.5-10 wt%.
2. The method for preparing a high coulombic efficiency silicon carbon negative electrode material as claimed in claim 1, wherein the silicon oxide in the raw material is micron-sized; the alloy powder is in a micron-sized particle size, and the particle size of the alloy powder is 1/3-1/5 of the particle size of the silicon oxide.
3. The method for preparing a high coulombic efficiency silicon carbon negative electrode material as claimed in claim 1, wherein the mixing in the first step is grinding in a ball mill for 1-10 h.
4. The method for preparing a high coulombic efficiency silicon carbon negative electrode material as claimed in claim 1, wherein the atmosphere in the redox reaction is a vertical furnace or a horizontal box furnace, and the oxygen content is controlled to be less than 20ppm during the heat treatment; in the oxidation-reduction reaction, gas is firstly vacuumized and replaced for 3-5 times, and then heating is started.
5. The method for preparing a silicon-carbon anode material with high coulombic efficiency as claimed in claim 1, wherein the acid washing in step three is hydrochloric acid or nitric acid.
6. The method of claim 1, wherein the carbon source gas is deposited in the vapor phase deposition at a flow rate of 5 to 100sccm in a range of 5 to 30%.
7. The method for manufacturing a silicon-carbon negative electrode material with high coulombic efficiency as claimed in claim 1, wherein the oxygen content of the silicon oxide SiOx in the starting material is measured by using an oxygen content analyzer as a tool, and the reduction degree of the silicon oxide SiOx is determined by calculating the x value before and after the reaction.
8. The silicon-carbon anode material prepared by the method of any one of claims 1 to 7, wherein the silicon nanoparticles and the uniform buffer structure with controllable content are arranged inside, the first coulombic efficiency is more than 87%, and the specific capacity is more than 1400 mAh/g.
9. The application of the silicon-carbon negative electrode material as claimed in claim 8, wherein the silicon-carbon negative electrode material is used as a rate type lithium ion battery negative electrode material or a capacity type lithium ion negative electrode material.
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